Substituted 2, 6-substituted pyridine compounds

ABSTRACT

There are disclosed novel 2,6-substituted-3,5-pyridinedicarboxylic acids, esters, salts, amides, halides, and cyano compounds useful as herbicides, and as intermediates which provide herbicides.

This is a division of application Ser. No. 062,012, filed June 15, 1987,now U.S. Pat. No. 4,826,530, which is a division of application Ser. No.602,021 filed Apr. 24, 1984, now U.S. Pat. No. 4,692,184.

This invention relates to a new class of2,6-substituted-3,5-pyridinedicarboxylic acid derivatives having a widerange of activity as herbicides.

Pyridine derivatives have, for many years, been investigated for use inthe biological sciences. For example,2,6-bis-(trifluoromethyl)-4-pyridinols have been found useful asherbicides and fungicides as disclosed in U.S. Pat. No. 3,748,334. Suchcompounds are characterized by substitution in the 4-position by ahydroxyl radical. In addition to the hydroxyl radical, the pyridinenucleus may also be substituted with bromo, chloro or iodo radicals.Trifluoromethyl pyridine derivatives have also been disclosed in U.S.Pat. Nos. 2,516,402 and 3,705,170 wherein the nucleus is furthersubstituted by halogens as well as numerous other substituents. Some ofthese compounds are also noted to be useful as herbicides.

Also known because of their fungicidal activity are 4-substituted2,6-dichloro-3,5-dicyano-pyridines wherein the 4-position is substitutedwith alkyl, phenyl, naphthyl or pyridyl groups. Such compounds aredisclosed in U.S. Pat. No. 3,284,293, while similar compounds aredisclosed in U.S. Pat. No. 3,629,270 wherein the 4-position issubstituted with a heterocyclic group wherein the hetero atom is oxygenor sulfur.

In EPO Pat. No. 44,262, there is disclosed2,6-dialkyl-3-phenylcarbamyl-5-pyridinecarboxylates and-5-cyano-compounds useful as herbicides. There is no disclosure of the2-haloalkyl radicals nor any substitution in the 4-position of thepyridine ring.

The pyridine derivatives have also received attention in the search fornew herbicides and have been reported in U.S. Pat. Nos. 1,944,412,3,637,716, and 3,651,070. All of these patents disclose polyhaloderivatives of dicarboxypyridines. All have in common the directsubstitution on a ring carbon by a halogen in the 3- and 5-positionswhile the 2- and 6-positions are occupied by carboxylate groups. The4-position is open to substitution by a wide range of materialsincluding halogens, hydroxy radicals, alkoxy, and carboxyl groups. Suchcompounds have found utilization as herbicides, bactericides, andfungicides. When the 4 position is occupied by a silver salt, U.S. Pat.No. 1,944,412 discloses that such compounds have been utilized in theproduction of X-ray pictures with intraveneous injection of suchcompounds.

BRIEF DESCRIPTION OF THE INVENTION

It is an object cf this invention to provide herbicidal methodsutilizing the novel pyridines of this invention.

Another object of this invention is to provide novel methods forpreparing the novel compounds of this inventor and novel intermediatesuseful therein.

The novel compounds of this invention are useful as herbicides orintermediates which provide herbicides and represented by Formula I##STR1## wherein:

R is selected from the group consisting of lower alkyl, lower alkenyl,lower alkynyl, lower alkenylakyl, haloalkyl haloalkenyl, C₃₋₇cycloalkyl, C₃₋₆ cycloalkanylalkyl, C₃₋₆ cycloalkenyl, aryl, arylmethyl,alkoxyalkyl, benzyloxymethyl, alkylthioalkyl, dialkoxyalkyl,(1-alkoxy-1-alkylthio)alkyl, aminoalkyl, alkylaminoalkyl,dialkylaminoalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, alkylsubstituted with a dialkyl sulfonium salt, cyanoalkyl, carbamylalkyl,carbalkoxyalkyl, carbalkoxyalkenyl, formylalkyl, dialkylaminoalkenyl,saturated and unsaturated heterocyclic radicals having from 3 to 6 atomsin the ring including from 1 to 3 hetero atoms selected from O, S, andN, and wherein the radical is joined to the pyridine ring by a C-C bond,and lower alkyl substituted with a saturated or unsaturated heterocyclicradical wherein the hetero atom is selected from O, S, and N;

R₁ and R₂ are independently selected from alkyl, fluorinated methyl, andchlorofluorinated methyl radicals, provided that one of R₁ and R₂ mustbe a fluorinated methyl or chlorofluorinated methyl radical; and

X and Y are independently selected from the group consisting of ##STR2##wherein Z is selected from O and NR₇ where R₇ is hydrogen or loweralkyl, and wherein R₃ is selected from O And S wherein R₃ in eachoccurrence is independently selected from hydrogen, alkyl C₁₋₄,alkenylyalkyl C₃₋₄, haloalkyl C₁₋₄, cycloalkanylalkyl, cyanoalkyl, oralkynylalkyl C₃₋₄ ; ##STR3## wherein

R₄ is selected from hydrogen and halogen, ##STR4## wherein

R₅ and R₆ are independently selected from hydrogen, lower alkyl, andphenyl;

--CH₂ OH; and

--C.tbd.N.

Compounds of this invention which are of particular interest asherbicides include those of the above Formula I wherein X and Y are bothester groups in which R₃ n each ester group is independently an alkylgroup having 1-3 carbon atoms. Of these preferred 3, 5 diestercompounds, a more preferred grouping in those compounds in which R₁ andR₂ are dissimilar fluorinated methyl radicals; and within this morepreferred grouping, the most preferred compounds are those which R is analkyl or alkylthioalkyl substituent having 1-5 carbon atoms.

The term "alkyl" means herein both straight and branched chain radicalswhich include, but are not limited to, ethyl, methyl, n-propyl,1-ethylpropyl, 1-methylpropyl, n-butyl, 2,2-dimethylpropyl, pentyl,isobutyl, isopropyl. The term "cycloalkyl" is intended to meancycloalkyl radicals such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, and cycloheptyl.

The term "lower alkyl" herein means an alkyl radical having 1 to 7carbon atoms. The terms "lower alkenyl" and "lower alkynyl" herein meanalkenyl and alkynyl groups having 2 to 7 carbon atoms. Examples of suchalkenyl groups include ethenyl, 1-propenyl, 2-propenyl, 1-butenyl,2-butenyl, 3-butenyl, 2-methyl1-propenyl, 2-methyl-2-propenyl,1-methylethenyl, and the like. Examples of such lower alkynyl groupsinclude ethynyl, 1-propynyl, 2-propynyl, and so forth.

The term "saturated and unsaturated heterocyclic radicals" meansheterocyclic radicals having from 3 to 6 atoms ir. the ring includingfrom 1 to 3 hetero atoms selected from O, S, and N, and typicallyinclude, but are not limited to, furyl, pyridyl, thienyl, thiiranyI,oxiranyl, and aziridinyl.

The term "cycloalkanylalkyl" is intended to mean alkyl radicalssubstituted with a C₃₋₆ cycloalkyl radical. The term "haloalkyl" isintended to mean alkyl radicals substituted with one or more halogenatoms.

The term "fluorinated methyl" means herein methyl radicals having one ormore fluorine atoms attached thereto including radicals wherein allhydrogen atoms substituted by fluorine.

The term "chlorofluorinated methyl" means herein a methyl radical havingat least one hydrogen substituted by fluorine and at least one otherhydrogen substituted by chlorine.

DETAILED DESCRIPTION OF THE INVENTION Preparation of SymmetricalPyridines

Scheme I below describes a method whereby symmetrical pyridines (D) ofthis invention may be produced. They are conveniently obtained fromdihydropyridines (C) which are, in turn, obtained from the correspondingdihydroxypieridines (B) by dehydration. Suitable dehydration agents are,for example, but not limited to, sulfuric acid, toluenesulfonic acid andtrifluoroacetic anhydride. Typically, the dihydroxypiperidines (B) areobtained from the corresponding dihydroxytetrahydropyrans (A) bytreatment with aqueous cr gaseous ammonia. To provide the desireddihydrcxytetrahydropyran (A), the appropriate aldehyde is reacted withan appropriate 3-ketoester and a catalytic amount of a base such aspiperidine or KF in a suitable reaction medium. This reaction providesthe dihyroxytetrahydropyran from which is obtained by reaction with NH₃or NH₄ OH the dihydroxypiperidine which, in turn, provides thedihydropyridine (C) by dehydration. Isolation of thedihydroxytetrahydropyran and dihydroxypiperidine intermediates isunnecessary in this reaction scheme, although the intermediate may beisolated as in some of the following Examples. Oxidation of thedihydropyridine (C), as mentioned above, provides the symmetricalpyridines (D) of this invention. Reaction Scheme 1 further illustratesthe reaction scheme.

When providing the dihydropyridine compounds wherein the 4-position issubstituted by either an aryl, arylmethyl, phenylmethoxymethyl orheterocyclic radicals wherein the hetero atom is oxygen or sulfur, it ispreferred to utilize a catalytic amount of an organic acid as thedehydration agent in place of the usual inorganic acid. Typically,toluenesulfonic acid in a reaction medium of, for example, toluene, hasbeen found to be suitable for this purpose. The reaction is generallyrun at reflux temperature and water is removed by azeotropicdistillation. To provide a major amount of the 3,4-dihydropyridineisomers from the corresponding piperidine, trifluoroacetic anhydride isthe preferred dehydration agent. In said process, the reaction medium istypically a chlorinated hydrocarbon such as methylene chloride. ##STR5##

The above Scheme I conveniently provides symmetrical diesters of 2,6-bissubstituted-3,5-pyridine-dicarboxylic acids represented by the Formula(D).

Diester compounds of Formula I which are represented by the followingformula: ##STR6## wherein R, R₁, R₂ and R₃ are each defined as above,with the exception that R₁ and R₂ cannot both be CF₃ and wherein each R₃is equal and cannot be hydrogen, can be prepared by a noveldehydrofluorination reaction reacting an equimolar mixture of thecorresponding dihydropyridine wherein one of R₁ and R₂ has one morefluorine than product and a nonaqueous organic base such as1,8-diazabicyclo-[5.4.0]-undec-5-ene (DBU) or 2,6-lutidine,trialkylamines, and pyridine or mono-, di-, and tri-alkylsubstitutedpyridine in the presence of catalytical amounts of DBU either neat or ina suitable solvent such as tetrahydrofuran, or aromatic solvent such astoluene.

Similarly, diester compounds of Formula II in which one of R₁ and R₂ hastwo fewer fluorines than the other (i.e., one of R₁ and R₂ is CF₃ andthe other is CFH₂) are prepared by the further reduction of the compoundthus prepared as follows: The compound of Formula II in which one of R₁and R₂ is CF₃ and the other is CF₂ H is reduced to the corresponding1,2-dihydropyridine using as a strong reducing agent an alkali metalborohydride such as sodium borohydride in any suitable solvent,preferably N,N-dimethylformamide. The dihydropyridine so obtained isthen once again dehydrofluorinated using a nonaqueous organic base suchas DBU or 2,6-lutidine in an appropriate solvent such as diethyl etheror tetrahydrofuran to the corresponding pyridine compound in which oneof R₁ and R₂ is CF₃ and the other is CFH₂. If desired, this sodiumborohydride reduction/dehydrofluorination sequence may be repeated toform a pyridine compound in which one of R₁ and R₂ is CF₃ and the otheris CH₃, again proceeding by way of a 1,2-dihydropyridine intermediate.

These novel and unexpected reactions are used herein to provideunexpectedly effective herbicides of this invention.

The mono-acid compounds represented by the following Formula III##STR7## (wherein R, R₁, R₂ and R₃ are each as defined in Formula Iabove) can be derived from compounds of Formula (D) or II by partial (orselective) hydrolysis. It has been discovered that when R₂ in FormulaIII is a difluoromethyl radical (-CHF₂) and R₁ is not a difluoromethylradical, the ester group adjacent the difluoromethyl radical isselectively removed by the hydrolysis procedure, leaving the ester groupadjacent R₁ intact.

To prepare a compound of Formula I wherein the 3,5-ester groups aredissimilar, there is first prepared a compound represented by thefollowing Formula IV: ##STR8## wherein R, R₁, R₂ and R₃ have the samemeaning as in Formula I above and Hal means halogen selected fromchlorine, bromine, and fluorine.

Compounds of Formula IV above can be prepared by mixing a compound ofFormula III above with excess thionyl halide or other suitable agent andholding the mixture at reflux for several hours. Compounds of Formula IVare refluxed with an appropriate alcohol for several hours. The desiredproduct is recovered by known methods to give the desired compound ofFormula I above wherein X and Y are dissimilar esters.

Alternatively, a mixture of a compound of Formula III and an excess cfan appropriate alkyl halide is stirred in a suitable solvent such asN,N-dimethylformamide (DMF) or acetone with 4 equivalents of potassiumfluoride or one equivalent of potassium carbonate as the base. Afterconstant stirring for about 16 hours, the residue is poured into waterand extracted with solvent. The solvent extract is dried andconcentrated to give the unsymmetrical dicarboxylic acid diester.

To provide the pyridinedicarboxylic acid of the Formula V ##STR9##wherein R, R₁ and R₂ have the same meaning as in wherein Formula Iabove, an appropriate pyridinedicarboxylic acid diester is mixed with anexcess of appropriate base and a suitable solvent. This mixture is heldat reflux for several hours and concentrated. After concentration, thedesired product is recovered and purified by known methods to providethe desired pyridinedicarboxylic acid. The symmetrical dicarboxylic acidcan also be obtained by the hydrolysis of the corresponding ester in themanner described above. Usually recrystallization from an appropriatesolvent adequately purifies the product.

Compounds of this invention represented by the following Formula VI:##STR10## (wherein R, R₁ and R₂ are defined above) can be prepared byreacting a compound of Formula V with an excess of thionyl or phosphorushalide at reflux conditions for several hours. The product isconcentrated and dried.

The symmetrical diester compound of Formula I can also be provided bythe reaction of a compound of Formula VI with the appropriate alcohol atreflux conditions for a period of time such as from 15-20 hours.Alternatively, a mixture of one equivalent of a compound of Formula VI,an excess of an appropriate alkyl halide and two equivalents ofpotassium carbonate is stirred in suitable solvent such asN,N-dimethylformamide for several hours and then poured into water. Thedesired product is recovered by known methods of solvent extraction andpurification.

As can be seen from the above, the appropriate ester is prepared fromthe corresponding carbonyl chloride by admixture with the appropriatealcohol to provide the desired ester. This can be performed for both thesymmetrical and unsymmetrical compounds of the above-described formula.

Compounds of this invention represented by Formula VII: ##STR11##(wherein R, R₁, R₂, R₃, R₅ and R₆ are as defined above in Formula I) areprepared by reacting a compound of Formula IV with an appropriate amountof amine or ammonia. The procedure is demonstrated in Examples 88 and 89below.

Compounds of this invention represented by formula VIII: ##STR12##(wherein R, R₁, R₂, R₃, R₅ and R₆ are as defined above in Formula I) areprepared by reacting an excess of the appropriate amine or ammonia witha compound of Formula VI. The procedure is similar to that of Examples88 and 89 below.

Compounds of this invention represented by formula IX: ##STR13##(wherein R, R₁, R₂, and R₃ are as defined in Formula I above) can beprepared by reacting a compound of Formula VII, wherein R₅ and R₆ areboth hydrogen, with an excess of dehydration agent such as phosphorusoxychloride at reflux. The procedure is demonstrated in of Examples 92and 93 below.

Compounds of this invention represented by formula X. ##STR14## (whereinR, R₁, R₂, and R₃ are as defined in Formula I above) are prepared byreacting a compound of Formula III with an excess of reducing agent suchas borane in a suitable solvent. The procedure is demonstrated inExample 96 below.

Compounds of this invention represented by formula XI: ##STR15##(wherein R, R₁, R₂, and R₃, are as defined above in Formula I) can beprepared by reacting a compound of Formula X with a suitable oxidantsuch as pyridinium chlorochromate in a suitable solvent such asmethylene chloride. The procedure is demonstrated in Example 97 below.

Compounds of this invention represented by the formula XII: ##STR16##(wherein R and R₁ are R₂, defined in Formula I above) are prepared byreacting a compound of Formula VIII, wherein R₅ and R₆ are hydrogen,with excess phosphorus oxychloride at reflux. The procedure is similarto that of Example 92.

Compounds of this invention represented by formula XIII: ##STR17##(wherein R, R₁ and R₂, are as defined in Formula I above) can beprepared by reacting a compound of Formula V with excess borane in aprocedure similar to that described in Example 96 below.

Compounds of this invention represented by the formula XIV ##STR18##(wherein R, R₁, R₂, and R₃ and R₃ are as defined in Formula I above) areprepared by reacting a compound of Formula XIII with two equivalents ofa suitable oxidant such as pyridinium chlorochromate in a proceduresimilar to that described in Example 97 below.

Thioester compounds of this invention having the following Formula XV:##STR19## are prepared by reacting an appropriate thiol with a compoundof the Formula IV above in the same manner as the preparation of anordinary ester.

Similarly, dithioesters represented by the following Formula XVI:##STR20## are prepared by reaction of a compound of the Formula VI abovewith an appropriate thiol. In general, preparation of the variousthioester types parallels preparation of the esters described above.Thioesters are exemplified in Examples 140-149.

Imidate compounds of this invention represented by the Formula XVII:##STR21## are prepared from the corresponding amide of Formula via thereaction of the amide with thionyl chloride to form a chloroimide,followed by reaction of the chloroimide with an alcohol. This procedureis exemplified in Example 152.

Preparation of the compounds of this invention will become more clearupon examination of the following examples in which, for the most part,the preparation of the dihydroxytetrahydropyran (A), thedihydroxypiperidine (B), and the dihydropyridine (C) precursors isexemplified in detail in a stepwise manner, isolating each precursorbefore beginning the synthesis of the next. However, a particularlypreferred synthesis of the dihydropyridine, precursor compounds isachieved according to Example jj below (the "one pot synthesis") withoutisolation of the dihydroxytetrahydropyran and dihydroxypiperidineprecursors. According to this preferred method to provide the desireddihydropyridines, there is provided a first reaction wherein a mixtureof two equivalents of an appropriate 3-ketoester, one equivalent of anappropriate aldehyde and a catalytic amount of piperidine is allowed toreact at 40°-100° C. neat or in a suitable solvent (such as methylenechloride or toluene) for a period of 4-20 hours. After the reaction iscompleted as indicated by ¹⁹ F NMR analysis, suitable solvent is addedto the product and gaseous ammonia is passed through the mixture untilthe second reaction is completed. The reaction mixture is then purgedwith nitrogen to remove excess ammonia. The reaction mixture is thencooled with an ice-water bath to 5°-10° before treatment with ice-waterbath to concentrated sulfuric acid. After the reaction mixture isstirred for a period of 10 minutes to 2 hours, the mixture is pouredonto crushed ice, the methylene chloride layer is separated, dried andconcentrated to provide the desired dihydropyridines. In this mode ofoperation, the desired dihydropyridines is produced in one reactionvessel without isolation of the precursor, dihydroxytetrahydropyran anddihydroxypiperidine. The desired dihydropyridine is therefore obtainedin better yield.

To provide the dihydroxytetrahydropyran, precursor of Structure A, theprocedure of Day et al as described in the Journal of Organic Chemistry,Vol. 30, page 3237 (1965) may be employed. According to this procedure,an appropriate aldehyde is reacted with an appropriate 3-ketoester and acatalytic amount of piperidine with or without a suitable reactionmedium.

PREPARATION OF DIHYDROXYTETRAHYDROPYRANS

The following examples a-m provide typical procedures for preparation ofprecursor compounds of structure (A) shown in Schedule I above.

EXAMPLE a Preparaton of diethyl2,6-bis(trifluoro-methyl)-2,6-dihydroxy-4-propyl-tetrahydro-3,5-pyrandicarboxylate

A 500 ml single necked flask is charged with 20 g (0.278 mole) ofbutyraldehyde, 102 g (0.555 mole) of ethyl trifluoroacetoacetate andapproximately 150 ml of ethanol. To this is added 3 g (0.0156 mole) ofpotassium fluoride. The mixture is stirred at room temperature for 18hours. The material is concentrated and diluted with ethyl ether. Theorganics are washed with water, dried and concentrated to give a whitepowder. The crude product is recrystallized from hot methyl cyclohexaneto give 13 g (10.7%) of product m.p. 128°-132° C.

Anal. Cal'd for C₁₆ H₂₂ O₇ F₆ : C, 43.63; H, 5.00 Found: C, 43.58; H,5.04.

EXAMPLE b

Preparation of dimethyl 2,6-bis(trifluoro-methyl)-2,6dihydroxy-4-isobutyl-tetrahydro-3,5-pyrandicarboxylate

To a mechanically stirred mixture of 280 g (2.0 mole) of 80% pure methyltrifluoroacetoacetate and 86 g (1.0 mole) of isovaleraldehyde is added 1ml of piperidine. An exothermic reaction occurs and the temperature ofthe reaction mixture reaches 105° C. After 5 hours of stirring, thereaction mixture is triturated with 450 ml of hexane and 30 ml of etherand cooled with a dry ice bath to give 1.68 g of a first crop, m.p.83°-87° C. and 14.51 g of a second crop, m.p. 67°-73° C.

The first crop is the desired product which contains a mixture of 5:1cis and trans isomers.

Anal. Calc'd for C₁₅ H₂₀ F₆ O₇ : C, 42.26; H, 4.73Found: C, 42.54; H,4.77

The second crop is a 2:1 mixture of cis and trans isomers. The motherliquor is concentrated to give 344 g of a residue which is a crudemixture of cis and trans isomer of the desired product.

The cis isomer has a structure A1 with the two esters groups cis to eachother whereas the trans isomer has a structure A2 with the two estergroups trans to each other as shown below: ##STR22##

Additional compounds are prepared according to the procedure describedin Example a and listed in Table 1 by reacting the appropriate aldehydewith the appropriate trifluoroacetoacetate.

                                      TABLE 1                                     __________________________________________________________________________    PREPARATION OF DIHYDROXYTETRAHYDROPYRANS                                       ##STR23##                           (A)                                                              C       H                                             Example                                                                            R            mp °C.                                                                       Calc'd                                                                            Found                                                                             Calc'd                                                                            Found                                     __________________________________________________________________________    c    CH.sub.2 CH.sub.3                                                                          123-127                                                                             42.25                                                                             42.41                                                                             4.69                                                                              4.72                                      d    CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        45-61 44.93                                                                             45.16                                                                             5.28                                                                              5.27                                      e    CH(CH.sub.3).sub.2                                                                         88-98 43.63                                                                             43.72                                                                             5.00                                                                              5.05                                      f    CH.sub.2 CH(CH.sub.3).sub.2                                                                87-90 44.95                                                                             45.02                                                                             5.28                                                                              5.20                                      g    CH(CH.sub.2 CH.sub.3).sub.2                                                                105-111                                                                             46.15                                                                             46.23                                                                             5.55                                                                              5.66                                            ##STR24##    98-101                                                                             43.84                                                                             43.96                                                                             4.60                                                                              4.52                                      i                                                                                   ##STR25##   100-103                                                                             47.60                                                                             47.38                                                                             5.26                                                                              5.63                                      j                                                                                   ##STR26##   120-125                                                                             49.07                                                                             49.79                                                                             4.70                                                                              4.42                                      k                                                                                   ##STR27##   90-93 49.03                                                                             49.45                                                                             4.71                                                                              4.71                                      l    CH.sub.2 OCH.sub.3                                                                         77.5-81                                                                             40.73                                                                             40.69                                                                             4.56                                                                              4.71                                      m                                                                                   ##STR28##   128-136                                                                             48.11                                                                             47.68                                                                             4.25                                                                              4.07                                      __________________________________________________________________________

Preparation of Dihydroxypiperidines

To provide the dihydroxypiperidine precursor (B), four different methodsmay be employed. The first method (Method I) employs the procedurewherein a mixture of two equivalents of a 3-ketoester, one equivalent ofan appropriate aldehyde and 1.5 equivalents of ammonium hydroxide isrefluxed in ethanol for 4-18 hours and reconcentrated to provide Bsimilar to the literature procedure.

In the second method (Method II), (Journal of Heterocyclic Chemistry,Vol. 17, 1109 (1980)), a mixture of one equivalent ofdihydroxytetrahydropyran of structure A, 1.5 equivalents of aqueousammonium hydroxide and a suitable amount of ethanol is stirred at roomtemperature or held at reflux for 4-18 hours and concentrated. Theresidue is recrystallized from the appropriate solvent or purified inanother suitable manner to provide (B).

In the third method (Method III), a stream of gaseous ammonia is passedthrough a solution of dihydroxytetrahydropyran of structure (A) in asuitable solvent (such as tetrahydrofuran, toluene, or methylenechloride) for several hours until the ¹⁹ F NMR analysis indicates acomplete reaction. The reaction mixture is concentrated and the residueis recrystallized from an appropriate solvent otherwise purified asappropriate to provide the precursor of structure (B).

In the fourth method (Method IV), a mixture of two equivalents of anappropriate 3-ketoester, one equivalent of an appropriate aldehyde and acatalytic amount of piperidine is stirred with or without an appropriatesolvent at 40°-100° for a period of from several hours to several daysuntil the ¹⁹ F NMR analysis indicates a complete reaction. Aftercompletion of the above first step of Method IV, an appropriate solventis added to the above reaction mixture if the first step reaction iscarried out without a solvent. A stream of anhydrous ammonia gas ispassed through the solution at 40°-70° C. until the ¹⁹ F NMR indicates acomplete reaction (usually in the period of about six to ten hours). Thereaction mixture is concentrated and the residue is recrystallized froman appropriate solvent to provide the precursor structure (B).

Method IV is the preferred method because it provides higher yield ofthe desired product.

To further illustrate Methods I-IV, the following examples n-ff areprovided.

EXAMPLE n Preparation of dimethyl2,6-bis(trifluoromethyl)-2,6-dihydroxy-4-isobutyl-3,5-piperidinedicarboxylate

To a solution of 344 g (0.920 mole) crude product from Example b in 500ml of tetrahydrofuran (THF) is passed 58 g (3.41 mole) of gaseousammonia for 3 hours. The reaction mixture is concentrated and theresidue (332 g) is recrystallized from hexaneether to give 53.7 g (13%yield from methyl trifluoroacetoacetate) of the desired product as awhite solid, m.p. 102°-106° C.

Anal. Calc'd for C₁₅ H₂₁ F₆ N_(1pk) O₆ : C, 42.36; H, 5.00; N, 3.29;Found: C, 42.84; H, 4.94; N, 3.29

The mother liquor is concentrated to provide more of the crude desiredproduct.

EXAMPLE o Preparation of diethyl2,6-bis(trifluoromethyl)-2,6-dihydroxy-4-(2-furyl)-3,5-piperidinedicarboxylate

A 500 mL 3 necked flask is charged with 60 mL ethanol, 29.07 g (0.3mole) of 2-furaldehyde and 110 g (0.6 mole) of ethyltrifluoroacetoacetate. The reaction mixture is cooled in an ice bathbefore 21.15 21.15 g (0.35 mole) of aqueous ammonium hydroxide is addedslowly with stirring. The mixture is heated at reflux for 2 hours andcooled. The resulting precipitate is filtered and recrystallized fromhot ethanol to give 53.34 g (39%) of crystals, m.p. 129°-131° C.

Anal. Calc'd C₁₇ H₁₇ F₆ N₁ O₇ : C, 44.06; H, 4.10; N, 3.02; Found: C,44.04; H, 4.12; N, 3.03.

EXAMPLE p Preparation of diethyl2,6-bis(trifluoromethyl)-2,6-dihydroxy-4-propyl-3,5-piperidinedicarboxylat

A 500 ml round bottomed flask was charged with 150-200 mL of ethanol and40 g (0.0909 mole) of product of Example a. The mixture is stirred by amagnetic stirrer while 8.23 g (0.136 mole) of 58% aqueous ammoniumhydroxide is added slowly to the flask. The mixture is stirred for 18hours under nitrogen. The precipitate is filtered to yield 17.83 g(44.68%) of the desired product, m.p. 140°-142° C.

Anal. Calc'd for C₁₆ H₂₃ O₆ N₁ F₇ : C, 43.73; H, 5.23; N, 3.18; Found C,43.67; H, 5.26; N, 3.19.

EXAMPLE q Preparation of trans-diethyl2,6-bis-(difluoromethyl)-2,6-dihydroxy-4-isobutyl-3,5-piperidinedicarboxylate.

To a mixture of 25.0 g (0.150 mole) of ethyl difluoroacetotoacetate(EDFAA) and 8.04 ml (0.075 mole) of isovaleradehyde is added to 2 ml ofpiperidine. The reaction mixture becomes exothermic and temperature ofthe mixture reaches 86°. After the temperature of the reaction mixturehas subsided to room temperature, the reaction mixture is treated withTHF (100 ml). Gaseous NH₃ is passed through the above THF solution until¹⁹ F NMR indioates a complete reaction. The reaction mixture isconcentrated to 32.77 g (100%) of an oil which contains the desiredproduct and its cis isomer. This oil is crystallized from hexane to givea solid. Part of this solid (5.0 g) is dissolved in ether. The ethersolution is washed with water, dried (MgSO₄) and concentrated to an oilwhich crystallized upon standing. Recrystallization from hexane gives1.0 g (22.8%) of this desired product as a white solid, m.p. 98°-100° C.This material is identified as the trans isomer by ¹⁹ F NMR.

Anal Calc'd for C₁₇ H₂₇ F₄ NO₆ : C, 48.92; H, 6.52; N, 3.36; Found: C,48.93; H, 6.51; N, 3.31

EXAMPLE r Preparation of diethyl2,6-bis(trifluoromethyl)-2,6-dihydroxy-4-butyl-3,5-piperidinedicarboxylate

To a 500 mL 3-necked flask is charged 40 g (0.0881 mole) of the productof Example d in Table 1 and about 200-250 mL of THF. The flask is fittedwith 2 dry ice condensers and a nitrogen inlet. Ammonia gas, 5 g (0.294mole) is bubbled into the solution and the solution is stirred for 18hours. The organics are concentrated, diluted with ethyl ether, washedin water, dried over anhydrous MgSO₄ and concentrated. The residue istriturated with n-hexane and filtered to give 7.57 g (19%) of thedesired product, m.p. 77°-80° C.

Anal. Calc'd for C₁₇ H₂₅ F₆ N₁ O₆ : C, 45.03; H, 5.51; N, 3.09; Found:C, 44.96; H, 5.58; N, 3.03.

Additional examples of 2,6-dihydroxypiperidines of structure B above areprepared according to the above-described method of Examples n to r andare listed in Table 2.

                                      TABLE 2                                     __________________________________________________________________________    PREPARATION OF DIHYDROXYPIPERIDINES                                           __________________________________________________________________________     ##STR29##                                      (B)                                                      C       H       N                                  Example                                                                            R            mp °C.                                                                      n.sup.25                                                                          Calc'd                                                                            Found                                                                             Calc'd                                                                            Found                                                                             Calc'd                                                                            Found                          __________________________________________________________________________    s    CH.sub.3     133-135  41.07                                                                             41.28                                                                             4.15                                                                              4.25                                                                              3.42                                                                              3.35                           t    CH.sub.2 CH.sub.3                                                                          129-131  42.35                                                                             42.40                                                                             4.94                                                                              5.00                                                                              3.29                                                                              3.33                           u    CH(CH.sub.3).sub.2                                                                         85-89    43.74                                                                             44.08                                                                             5.28                                                                              5.13                                                                              3.19                                                                              2.74                           __________________________________________________________________________                               C       H       N                                  Example                                                                            R            mp °C.                                                                      n.sub.D.sup.25                                                                    Calc'd                                                                            Found                                                                             Calc'd                                                                            Found                                                                             Calc'd                                                                            Found                          __________________________________________________________________________    v    CH.sub.2 CH(CH.sub.3).sub.2                                                                69-73    45.03                                                                             45.20                                                                             5.51                                                                              5.50                                                                              3.09                                                                              3.11                                 ##STR30##   103-105  42.58                                                                             43.08                                                                             3.96                                                                              4.06                                                                              2.92                                                                              2.78                           x                                                                                   ##STR31##   179°                                                                            45.58                                                                             45.51                                                                             4.25                                                                              4.03                                                                              5.91                                                                              5.52                           y                                                                                   ##STR32##   133-135  45.58                                                                             45.59                                                                             4.25                                                                              4.28                                                                              5.91                                                                              5.90                           z    CH(CH.sub.2 CH.sub.3).sub.2                                                                86-89    46.25                                                                             46.67                                                                             5.82                                                                              5.79                                                                              3.00                                                                              3.17                           aa                                                                                  ##STR33##   134-141  49.28                                                                             50.38                                                                             4.72                                                                              4.67                                                                              2.87                                                                              2.78                           bb                                                                                  ##STR34##    99-101  48.21                                                                             47.96                                                                             4.27                                                                              4.25                                                                              2.96                                                                              2.79                           cc   CH.sub.2 CH.sub.2 SCH.sub.3                                                                55-73    40.76                                                                             40.81                                                                             4.92                                                                              4.86                                                                              2.97                                                                              3.10                           dd   CH.sub.2 OCH.sub.3                                                                         122-123  40.82                                                                             40.87                                                                             4.80                                                                              4.70                                                                              3.17                                                                              3.40                           ee   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3                                                            1.4269                                                                            43.50                                                                             43.82                                                                             5.37                                                                              5.30                                                                              2.98                                                                              3.14                           ff                                                                                  ##STR35##   102-109  48.75                                                                             48.74                                                                             4.87                                                                              4.87                                                                              2.71                                                                              2.71                           __________________________________________________________________________

Preparation of Dihydropyridines

The dihydropyridine precursors of structure (C) are obtained bydehydration of the corresponding dihydroxypiperidines with dehydrationagents such as concentrated sulfuric acid (Method V) or trifluoroaceticanhydride (Method VI) or by azeotropic removal of water usingp-toluenesulfonic acid as catalyst (Method VII).

To further illustrate the above-described Methods V-VII, the followingexamples gg-fff are provided.

EXAMPLE gg Preparation of a 2:1 mixture of dimethyl2,6-bis(trifluoromethyl)-1,4-dihydro-4-isobutyl-3,5-pyridine-dicarboxylateand its 3,4-dihydropyridine isomer

To an ice water cooled mixture of 200 ml of concentrated sulfuric acidand 200 ml of methylene chloride is added 48.7 g (0.115 mole) of theproduct of Example n at once. The reaction mixture is stirred for 20minutes and poured into 1 L. of ice water. The methylene chloride layeris separated and washed once with 100 ml of saturated sodiumbicarbonate, dried and concentrated to give 28.0 g (64.6%) of crudeproduct. A portion (5.0 g) of this product is kugelrohr distilled at 0.5torr (pot temperature at 120° C.) to give 4.8 g of the desired product,n_(D) ²⁵ 1.4391.

Anal. Calc'd for C₁₅ H₁₇ F₆ N₁ O₄ : C, 46.28; H, 4.40; N, 3.60; Found:C, 46.39; H, 4.44; N, 3.60.

EXAMPLE hh Preparation of diethyl2,6-bis(difluoromethyl)-1,4-dihydro-4-isobutyl-3,5-pyridinedicarboxylate

A 5.0 g (0.012 mole) crude cis and trans mixture of the product ofExample q is stirred with 10 ml of trifluoroacetic anhydride. Thetemperature of the reaction mixture rises to 36° C. After thetemperature subsides to room temperature, the reaction mixture isconcentrated. The residue is dissolved in ether and washed withsaturated NaHCO₃, dried (MgSO₄) and concentrated to an oil (3.76 g,82.3%) which is chromatographed by HPLC using 10% ethylacetate/cyclohexane as eluent to give 1.73 g (37.8%) of the desiredproduct as an oil, n_(D) ²⁵ 1.4716.

Anal. Calc'd for C₁₇ H₂₃ F₄ NO₄ : C, 53.54; H, 6.08; N, 3.67; Found: C,53.38; H, 6.40; N, 3.25.

EXAMPLE ii Preparation of diethyl2,6-bis(trifluoromethyl)-1,4-dihydro-4-(2-thienyl)-3,5-pyridinedicarboxylate

Approximately 100 ml of toluene is refluxed using a Dean-Stark trap toremove water. To the cooled toluene is added 20 g (0.0418 mole) of theproduct of Example w in Table 2 and 2.0 g (0.0105 mole) ofp-toluenesulfonic acid. The mixture is heated to reflux and refluxed for51/2 hours. The solution is cooled and filtered. The solvent is strippedoff and the product is chromatographed using 20% ethylacetate/cyclohexane as eluent. Wt. of product - 2.45 g (13.3%), n_(D) ²⁵1 4937.

Anal. Calc'd for C₁₇ H₁₅ O₄ N₁ F₆ S₁ : C, 46.04 ; H, 3.38; N, 3.16; S,7.22. Found: C, 46.11; H, 3.44; N, 3.12; S, 7.16.

In the preferred method to provide the desired dihydropyridines, thereis provided a first reaction wherein a mixture of two equivalents of anappropriate 3-ketoester, one equivalent of an appropriate aldehyde and acatalytic amount of piperidine is allowed to react at 40°-100° C. withor without a suitable solvent (such as methylene chloride) for a periodof 4-20 hours. After the reaction is completed as indicated by ¹⁹ F NMRanalysis, methylene chloride is added to the product and gaseous ammoniais passed through the mixture until the second reaction is completed.The reaction mixture is then purged with nitrogen to remove excessammonia. The reaction mixture is then cooled with an ice-water bath to5°-10° C. before treatment with concentrated sulfuric acid. After thereaction mixture is stirred for a period of 10 minutes to 2 hours, themixture is poured onto crushed ice, the methylene chloride layer isseparated, dried and concentrated to provide the desireddihydropyridines. In this mode of operation, the desired dihydropyridineis produced in one reaction vessel without isolation of theintermediates dihydroxytetrahydropyran and dihydroxypiperidine. Thedesired dihydropyridine is therefore obtained in better yield. Toillustrate the above-described procedure, the following examples areprovided.

EXAMPLE jj One pot synthesis of a mixture of diethyl2,6-bis(trifluoromethyl)-1,4-dihydro-4-ethyl-3,5-pyridinedicarboxylateand its 3,4-dihydropyridine isomer

A mixture of 368 g (2.0 mole) of ethyl trifluoroacetoacetate, 58 g (1.0mole) of propionaldehyde and 1 ml of piperidine in 400 ml of methylenechloride is stirred for 1 hr at 20° C. and then for 1 h at 30° C. andrefluxed for 1 hr and cooled. An additional 16.8 g (0.289 mole) ofpropionaldehyde is added to the above mixture and then refluxing iscontinued for 2 hrs. The heating mantle is removed. Through the reactionmixture is passed 108 g (6.35 mole) of ammonia gas in 2 hours. Thereaction mixture is stirred for 40 hours at 20° C. then cooled in icewater. To the reaction mixture is added carefully 100 ml of concentratedsulfuric acid in 20 minutes followed by an additional 300 ml ofconcentrated sulfuric acid in 10 minutes. The reaction mixture is pouredonto 600 g of crushed ice in a 4 L. beaker. The methylene chloride layeris separated, dried (MgSO₄) and concentrated to give 386 g of an oilwhich contains a mixture of the desired product and its 3,4-dihydroisomer. This oil is added to a vigorously stirred mixture of 300 ml ofconcentrated sulfuric acid and 300 ml of methylene chloride. The mixtureis stirred for 30 min. and poured onto 1 kg of ice. The methylenechloride layer is separated, dried (MgSO₄) and concentrated to give 348g of an oil which is triturated with 400 ml of petroleum ether to remove9.5 g of an insoluble solid. The petroleum ether filtrate is thenconcentrated. The residue is kugelrohr distilled at 0.4 torr to give 290g (74.5%) of an oil which is more than 90% pure of a mixture of thedesired product containing 1,4-dihydro (84%) and its 3,4-dihydro (16%)isomers determined by ¹⁹ F nmr analysis.

Additional examples of dihydropyridines of structure (C) in Scheme I areprepared according to the above-described methods in Examples gg to jjand are listed in Table 3. In all of the Examples in Table 3, R₃ isethyl.

                                      TABLE 3                                     __________________________________________________________________________    PREPARATION OF DIHYDROPYRIDINES                                                ##STR36##                                          (C)                                                      C       H       N                              Example                                                                            R            R.sub.1                                                                          1,4                                                                              3,4                                                                               n.sub.D.sup.25                                                                   Calc'd                                                                            Found                                                                             Calc'd                                                                            Found                                                                             Calc'd                                                                            Found                      __________________________________________________________________________    kk   CH.sub.3     CF.sub.3                                                                         100   1.4377                                                                            44.81                                                                             44.98                                                                             4.03                                                                              4.06                                                                              3.73                                                                              3.61                       ll   CH.sub.2 CH.sub.3                                                                          CF.sub.3                                                                         100   1.4441                                                                            46.27                                                                             46.41                                                                             4.37                                                                              4.19                                                                              3.59                                                                              3.62                       mm   CH.sub.2 CH.sub.2 CH.sub.3                                                                 CF.sub.3                                                                         100   1.4427                                                                            47.88                                                                             47.92                                                                             4.23                                                                              4.28                                                                              3.49                                                                              3.47                       nn   CH(CH.sub.3).sub.2                                                                         CF.sub.3                                                                         100   1.4440                                                                            47.64                                                                             47.69                                                                             4.71                                                                              4.75                                                                              3.47                                                                              3.46                       oo   CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        CF.sub.3                                                                         100   1.4414                                                                            48.95                                                                             48.95                                                                             5.03                                                                              5.09                                                                              3.35                                                                              3.35                       pp   CH.sub.2 CH(CH.sub.3).sub.2                                                                CF.sub.3                                                                         100   1.4420                                                                            48.92                                                                             48.78                                                                             5.03                                                                              5.06                                                                              3.35                                                                              3.31                       qq                                                                                  ##STR37##   CF.sub.3                                                                         100   1.4820                                                                            52.98                                                                             53.24                                                                             4.63                                                                              4.27                                                                              3.09                                                                              3.09                       rr                                                                                  ##STR38##   CF.sub.3                                                                         100   1.4720                                                                            47.77                                                                             47.83                                                                             3.51                                                                              3.51                                                                              3.27                                                                              3.25                       ss                                                                                  ##STR39##   CF.sub.3                                                                         100   (a) 49.31                                                                             49.33                                                                             3.65                                                                              3.72                                                                              6.39                                                                              6.39                       tt                                                                                  ##STR40##   CF.sub.3                                                                         100   (b) 49.31                                                                             49.32                                                                             3.65                                                                              3.68                                                                              6.39                                                                              6.35                       uu                                                                                  ##STR41##   CF.sub.3                                                                            100                                                                              1.4586                                                                            51.46                                                                             50.15                                                                             5.23                                                                              5.38                                                                              3.16                                                                              3.24                       vv                                                                                  ##STR42##   CF.sub.3                                                                         100   1.4845                                                                            52.40                                                                             52.48                                                                             4.40                                                                              4.42                                                                              2.91                                                                              2.92                       ww   CH.sub.2 OCH.sub.3                                                                         CF.sub.3                                                                         92 8  1.4436                                                                            44.45                                                                             44.26                                                                             4.23                                                                              4.40                                                                              3.46                                                                              3.22                       xx   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3                                                       CF.sub.3                                                                         85 15 1.4419                                                                            47.12                                                                             46.96                                                                             4.88                                                                              4.69                                                                              3.23                                                                              3.02                       yy   CH.sub.2 SCH.sub.3                                                                         CF.sub.3                                                                         89 11 1.4486                                                                            42.76                                                                             42.72                                                                             4.07                                                                              4.24                                                                              3.32                                                                              3.07                       zz   CH.sub.2 CH.sub.2 SCH.sub.3                                                                CF.sub.3                                                                         84 14 1.4688                                                                            44.14                                                                             44.12                                                                             4.40                                                                              4.19                                                                              3.22                                                                              3.05                       aaa  CH(CH.sub.2 CH.sub.3).sub.2                                                                CF.sub.3                                                                         100   1.4433                                                                            50.11                                                                             50.15                                                                             5.37                                                                              4.99                                                                              3.25                                                                              3.22                       bbb  CH.sub.2 CH.sub.2 CH.sub.3                                                                 CF.sub.2 H                                                                       100   1.4726                                                                            52.32                                                                             51.98                                                                             5.76                                                                              5.86                                                                              3.81                                                                              3.66                       ccc                                                                                 ##STR43##   CF.sub.2 H                                                                       100   (c) 56.02                                                                             56.16                                                                             6.18                                                                              6.42                                                                              3.44                                                                              3.42                       ddd                                                                                 ##STR44##   CF.sub.3                                                                         100   (d) 52.18                                                                             52.33                                                                             3.92                                                                              3.95                                                                              3.20                                                                              3.16                       eee                                                                                 ##STR45##   CF.sub.3                                                                         80 20 1.4417                                                                            48.92                                                                             49.05                                                                             5.07                                                                              5.10                                                                              3.36                                                                              3.34                       fff  CH.sub.2 C(CH.sub.3).sub.3                                                                 CF.sub.3                                                                         75 25 1.4393                                                                            50.12                                                                             50.19                                                                             5.37                                                                              5.37                                                                              3.25                                                                              3.20                       __________________________________________________________________________     (a) m.p. 171-172° C.                                                   (b) m.p. 136-138° C.                                                   (c) m.p. 40-44° C.                                                     (d) m.p. 42-45° C.                                                

The following examples illustrate, in a non-limiting manner, thepreparation of particular novel herbicides and intermediates for theproduction of herbicides in accordance with this invention.

To prepare the symmetrical 3,5-pyridinedicarboxylates according toScheme 1, the corresponding dihydropyridines C are treated with sodiumnitrite in acetic acid. The above described procedure is illustrated byExamples 1 to 11.

EXAMPLE 1 Preparation of diethyl2,6-bis(trifluoromethyl)-4-ethyl-3,5-pyridinedicarboxylates

A 250 ml flask is charged with 35 ml of glacial acetic acid and 13.89 g(0.0354mole) of diethyl2,6-bis-(trifluoromethyl)-4-ethyl-l,4-dihydro-3,5-pyridinedicarboxylate.Sodium nitrie is added in the amount of 3 g (0.0434 mole) and themixture is stirred for 72 hours under nitrogen. The solution is pouredover ice/water and stirred. The organics are extracted in ether andwashed with aqueous saturated sodium bicarbonate solution. Organics arethen dried on anhydrous magnesium sulfate, filtered and concentrated toyield 4.93 g (35.67%) of product, m.p. 33°-35° C.

Anal. Calc'd for C₁₅ H₁₅ O₄ N₁ F₆ : C, 46.51; H, 3.87; N, 3.61; Found:C, 46.54, H, 3.90; N, 3.63.

EXAMPLE 2 Preparation of diethyl2,6-bis(trifluoromethyl)-4-methyl-3,5-pyridinedicarboxylate

A 50 ml round bottomed flask is charged with 20 ml of glacial aceticacid. To this is added 5 g (0.0133 mole) of diethyl2,6-bis(trifluoromethyl)-4-methyl-l,4-dihydro-3,5-pyridinedicarboxylate,followed by a slow addition of 3 g (0.0434 mole) of sodium nitrite. Theflask is immediately fitted with a condenser and nitrogen line, thestirring continued for 18 hours, and the mixture is poured over crushedice and water. The organics are extracted twice with ether, washed oncewith saturated aqueous sodium chloride and washed twice with saturatedaqueous sodium bicarbonate solution. The organics are dried overanhydrous magnesium sulfate and concentrated yielding 2.16 g (43.5%) ofproduct, m.p. 55°-58° C.

Anal. Calc'd for C₁₄ H₁₃ F₆ NO₄ : C, 45.05; H, 3.48; N, 3.75; Found: C,44.95; H, 3.56; N, 3.75.

In a similar manner as described in Examples 1 and 2 above, butsubstituting the appropriate starting material and reaction conditions,other pyridinedicarboxylates are prepared. The same or equivalentsolvents, bases and catalysts, together with the appropriatetemperatures and times are readily used in these process embodiments.Typical other compounds prepared in accordance with the above procedureare shown in Table 4 together with certain of their physical properties.

                                      TABLE 4                                     __________________________________________________________________________    PREPARATION OF SYMMETRICAL                                                    3,5-PYRIDINEDICARBOXYLATES (D)                                                   Starting                                                                      Material                                                                   Ex.                                                                              Product of          Empirical                                                                              m.p.    Analysis                              No.                                                                              Example                                                                             Compound      Formula  °C.                                                                        n.sub.D.sup.25                                                                    Element                                                                            Calc'd %                                                                           Found                       __________________________________________________________________________                                                      %                           3  ddd   Diethyl 2,6-bis(trifluoro-                                                                  C.sub.19 H.sub.15 F.sub.6 N.sub.1 O.sub.4                                                  1.4696                                                                            C    52.42                                                                              52.47                                methyl)-4-phenyl-3,5-          H    3.47 3.51                                 pyridinedicarboxylate          N    3.22 3.20                        4  rr    Diethyl 2,6-bis(trifluoro-                                                                  C.sub.17 H.sub.13 F.sub.6 N.sub.1 O.sub.5                                              45-47   C    48.00                                                                              47.97                                methyl)-4-(2-furyl)-3,5-       H    3.05 3.08                                 pyridinedicarboxylate          N    3.29 3.29                        5  ii    Diethyl 2,6-bis(trifluoro-                                                                  C.sub.17 H.sub.13 F.sub.6 N.sub.1 O.sub.4 S.sub.1                                      48-50   C    46.25                                                                              46.13                                methyl)-4-(2-thienyl)-3,5-     H    2.94 2.94                                 pyridinedicarboxylate          N    3.14 3.14                                                                S    7.25 7.31                        6  mm    Diethyl 2,6-bis(trifluoro-                                                                  C.sub.16 H.sub. 17 O.sub.4 N.sub.1 F.sub.6                                                 1.4315                                                                            C    47.88                                                                              48.15                                methyl)-4-propyl-3,5-          H    4.23 3.85                                 pyridinedicarboxylate          N    3.49 3.47                        7  pp    Diethyl 2,6-bis(trifluoro-                                                                  C.sub.17 H.sub.19 O.sub.4 N.sub.1 F.sub.6                                                  1.4280                                                                            C    49.15                                                                              48.93                                methyl)-4-isobutyl-3,5-        H    4.57 4.66                                 pyridinedicarboxylate          N    3.37 3.45                        8  tt    Diethyl 2,6-bis(trifluoro-                                                                  C.sub.18 H.sub.14 O.sub.4 N.sub.2 F.sub.6                                                  1.4710                                                                            C    49.55                                                                              49.58                                methyl)-4-(3-pyridyl)-3,5-     H    3.23 3.26                                 pyridinedicarboxylate          N    6.42 6.37                        9  ss    Diethyl 2,6-bis(trifluoro-                                                                  C.sub.18 H.sub.14 O.sub.4 N.sub.2 F.sub.6                                                  1.4711                                                                            C    49.55                                                                              49.27                                methyl)-4-(4-pyridyl)-3,5-     H    3.23 3.27                                 pyridinedicarboxylate          N    6.42 6.47                        10 ww    Diethyl 2,6-bis(trifluoro-                                                                  C.sub.15 H.sub.15 F.sub.6 NO.sub.5                                                         1.4291                                                                            C    44.67                                                                              44.79                                methyl)-4-(methoxymethyl)-     H    3.75 3.78                                 3,5-pyridinedicarboxylate      N    3.47 3.44                        11 bbb   Diethyl 2,6-bis(difluoro-                                                                   C.sub.16 H.sub.19 F.sub.4 NO.sub.4                                                     22      C    52.60                                                                              52.63                                methyl)-4-propyl-3,5-          H    5.24 5.61                                 pyridinedicarboxylate          N    3.43 3.65                        __________________________________________________________________________

The following examples 12-27 illustrate a novel procedure of preparingcompounds of this invention represented by the Formula II.

EXAMPLE 12 Preparation of diethyl2-(difluoromethyl)-4-ethyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylate

A mixture of 1558 g (4.00 moles) of diethyl2,6-bis(trifluoromethyl)-l,4-dihydro-4-ethyl-3,5-pyridinedicarboxylate,628 g (4.0 moles) of 1,8-diazabicyclo-[5.4.0]-undec-5-ene (DBU), and 500ml of tetrahydrofuran is held at reflux for 19 hours, cooled and pouredinto a mixture of 2 kg of ice and 250 ml of concentrated hydrochloricacid. The organic layer is separated and the aqueous layer extractedwith 500 ml of CH₂ Cl₂ twice. The combined organic materials are dried(MgSO₄) and concentrated. The residue is kugelrohr distilled at 1 torr(pot temperature of 150°-160 ° C.) to give 1158 g (78.5%) of desiredproduct, n_(D) ²⁵ 1.4458.

Anal. Calc'd. C₁₅ H₁₆ F₅ NO₄ : C, 48.78; H, 4.37; N, 3.79; Found: C,48.75; H, 4.29; N, 3.72.

EXAMPLE 13 Preparation of diethyl2-(difluoromethyl)-4-n-propyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylat

A mixture of 20.0 g (0.05 mole) of diethyl2,6-bis(trifluoromethyl)-l,4-dihydro-4-n-propyl-3,5-pyridinedicarboxylate,7.62 g (0.05 mole) of DBU, and 200 ml of THF is held at reflux for 9hours, cooled an poured into 500 ml of ice water. The mixture isextracted with ether (2×200 ml). The ether extract is washed withdiluted hydrochloric acid, dried (MgSO₄), and concentrated to give 12.4g (64.5%) of the desired product, n_(D) ²⁵ 1.4436.

Anal. Calc'd. for C₁₆ H₁₈ F₅ N₁ O₄ : C, 50.13; H, 4.73; N, 3.65; Found:C, 49.92; H, 4.71; N, 3.58.

EXAMPLE 14 Preparation of dimethyl2-(difluoromethyl)-6-(trifluoromethyl)-4-isobutyl-3,5-pyridinedicarboxylate

(a) Reaction of the Product of Example gg with DBU

A mixture of 23.0 g (0.0591 mole) of the product of Example gg, 12.2 g(0.077 mole) of 96% pure DBU, and 100 ml of THF is held at reflux for 3days and poured into 250 ml of 3N HCl. The oil precipitate is extractedinto ether (2×100 ml). The ether extracts are dried (MgSO₄) andconcentrated to give 14.4 g of an oil which, according to ¹ H NMR,contained the desired product and acidic products. This oil is dissolvedin ether and extracted with 100 ml of saturated sodium bicarbonate. Theether layer is dried (MgSO₄) and concentrated to give 8.9 g of an oilwhich is 71% pure desired product (by ¹⁹ F NMR).

The sodium bicarbonate extract is acidified with concentrated HCl togive an oil which is extracted into ether. The ether layer is dried

(MgSO₄) and concentrated to give 4.8 g of a residue which containedmonocarboxylic acid and dicarboxylic acid (9:1) derived from the desiredproduct. This residue is treated with 3.0 g (0.0217 mole) of potassiumcarbonate, 20 ml of methyl iodide, and 50 ml of acetone. The mixture isheld at reflux for 42 hours and concentrated. The residue is treatedwith water and extracted with ether (2×100 ml). The ether layer is driedand concentrated. The residue is kugelrohr distilled at 1 torr (pottemperature of 130° C.) to give 5.1 g (23.4% from Example gg) of thedesired product as an oil, n_(D) ²⁵ 1.4478. This product crystallizesafter standing, m.p. 36°-37° C.

Anal. Calc'd. for C₁₅ H₁₆ F₅ N₁ O₄ : C, 48.79; H, 4.37; N, 3.79; Found:C, 48.75; H, 4.39; N, 3.77.

The 71% pure desired product described previously was chromatographed byHPLC using 3% ethyl acetate/cyclohexane as eluent to give an earlierfraction (0.79 g, retention time 7-8.5 min) which was identified asmethyl6-(difluoromethyl)-4-(isobutyl)-2-(trifluoromethyl)-3-pyridinecarboxylate.The second fraction (retention time 8.5-18.5 min) is an additional 6.4 g(29.4%) of pure desired product, n_(D) ²⁵ 1.447.

(b) Reaction of the Product of Example gg with Tributylamine

A mixture of 38.9 g of a 80% pure product of Example gg and 20.5 g oftributylamine is heated to 155° C. in 30 minutes. The reaction mixturewas cooled to 30° C. and diluted with 100 ml of toluene. The toluenesolution is washed successively with 6N hydrochloric acid, saturatedsodium bicarbonate, and brine, dried and concentrated to give 36.4 g ofa 73% pure product which corresponds to a 86% yield. This reaction canalso be carried out in excess of tributylamine (10 equivalent) givingessentially similar results.

(c) Reaction of the Product of Example gg with Tributylamine in Toluene

A mixture of 38.9 g of a 80% pure product of Example gg, 20.4 g oftributylamine and 30 ml of toluene is heated to 115° C. in 40 minutesand held at 115° C. for 1 hour and 40 minutes. The reaction mixture iscooled and worked up as in (b) to give 36.3 g of a 76% pure productwhich corresponds to a 90% yield.

(d) Reaction of the Product of Example gg with Triethylamine

A mixture of 11.8 g of a 80% pure product of Example gg and 3.34 g oftriethylamine is heated at 100° C. for 10 minutes, then at 125° C. for10 minutes. The reaction mixture was cooled and worked up as in (b) togive 8.14 g of a 76% pure product which corresponds to a 63% yield.

(e) Reaction of the Product of Example gg with 2,6-Lutidine in thePresence of a Catalytic Amount of DBU

A mixture of 5.0 g of product of Example gg and 2.13 g of 2,6-lutidineis heated at 143° C. for 30 minutes. Two drops of DBU is added and thereaction mixture is heated for additional 1 hour and 30 minutes, cooledand worked up as in (b) to give 4.23 g of the desired product. Thereaction can also be carried out in excess of 2,6-lutidine and catalyticamount of DBU without solvent or in the presence of toluene as solventgiving similar results.

EXAMPLE 15 Preparation of diethyl2-(difluoromethyl)-4-isopropyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylate

A mixture of 50.0 g (0.12% mole) of diethyl2,6-bis(trifluoromethyl)-l,4-dihydro-4-isopropyl-3,5-pyridinedicarboxylate,18.87 g (0.12% mole) of DBU and 200 ml of THF is held at reflux for 18hours and poured into water and extracted with ether. The ether extractis washed with diluted hydrochloric acid, dried (MgSO₄) andconcentrated. The residue is kugelrohr distilled at 1 torr to give 17.97g (37.8%) of the desired product which is a liquid, n_(D) ²⁵ 1.4465.

Anal. Calc'd. for C₁₆ H₁₈ F₅ N₁ O₄ : C, 50.13; H, 4.73; N, 3.65; Found:C, 50.16; H, 4.76; N, 3.65.

EXAMPLE 16 Preparation of diethyl2-(difluoromethyl)-4-isobutyl-6-(trifluoromethy1)-3,5-pyridinedicarboxylate

A mixture of 10.0 g (0.0240 mole) of diethyl2,6-bis(trifluoromethyl)-l,4-dihydro-4-isobutyl-3,5-pyridinedicarboxylate,3.65 g (0.0240 mole) of DBU and 150 ml of THF is held at reflux for 18hours and concentrated. The residue is dissolved in ether and washedwith diluted hydrochloric acid, dried (MgSO₄) and concentrated. Theresidue is kugelrohr distilled at 0.1 torr to give 4.80 g (50%) of thedesired product as an oil, n_(D) ²⁵ 1.4436.

Anal. Calc'd. for C₁₇ H₂₀ F₅ N₁ O₄ : C, 51.39; H, 5.07; N, 3.53; Found:C, 51.35; H, 5.08; N, 3.51.

EXAMPLE 17 Preparation of diethyl2-(difluoromethyl)-4-cyclopropyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylate

To a solution of 40 g (0.0916 mole) of diethyl2,6-bis(trifluoromethyl)-2,6-dihydroxy-4-cyclopropyl-tetrahydropyran-3,5-dicarboxylatein 200 ml of THF is introduced 55.5 g (3.26 moles) of ammonia. Thereaction mixture is concentrated to give 38.5 g (96.7%) of a solid. Aportion (28 g) of this material is stirred with 27.08 g (0.129 mole) oftrifluoroacetic anhydride for one day. The reaction mixture isconcentrated and diluted with ether. The ether solution is washed withsaturated sodium bicarbonate, dried (MgSO₄), and concentrated to give 21g (81.3%) of an oil, n_(D) ²⁵ 1.4460. This oil is identified as diethyl2,6-bis(trifluoromethyl)-4-cyclopropyl-1,4-dihydro-pyridine-3,5-dicarboxylate.A portion (18 g) of this oil and 150 ml of THF is treated with 6.82 g(0.0449 mole) of DBU. The reaction mixture is held at reflux for 24hours and concentrated. The residue is stirred with water and extractedwith ether. The ether extract is washed with diluted HCl, dried (MgSO₄),and concentrated. The residue is crystallized to give 13 g (76.0 %) ofcrude product. A portion (2.0 g) of this product is recrystallized frompetroleum ether at low temperature to give 1.17 g (85%) of desiredproduct, m.p. 30°-32° C.

Anal. Calc'd. for C₁₆ H₁₆ F₅ N₁ O₄ : C, 50.40; H, 4.23; N, 3.67; Found:C, 50.48; H, 4.32; N, 3.78.

In a manner similar to Example 12, other unsymmetrical pyridinecompounds of this invention are prepared as indicated in Table 5.

                                      TABLE 5                                     __________________________________________________________________________    PREPARATION OF UNSYMMETRICAL                                                  DIETHYL PYRIDINEDICARBOXYLATES                                                Ex.                                                                              Starting              Empirical                                                                              m.p.    Analysis                            No.                                                                              Material                                                                            Compound        Formula  °C.                                                                        n.sub.D.sup.25                                                                    Element                                                                            Calc'd %                                                                           Found                     __________________________________________________________________________                                                        %                         18 kk    Diethyl 2-(difluoromethyl)-                                                                   C.sub.14 H.sub.14 O.sub.4 N.sub.1 F.sub.5                                                  1.4410                                                                            C    47.33                                                                              47.25                              4-methyl-6-(trifluoromethyl)-    H    3.97 4.02                               3,5-pyridinedicarboxylate        N    3.94 3.87                      19 vv    Diethyl 2-(difluoromethyl)-                                                                   C.sub.21 H.sub.20 F.sub.5 N.sub.1 O.sub.5                                              48-51.5 C    54.67                                                                              54.43                              4-phenylmethoxymethyl-6-         H    4.37 4.17                               (trifluoromethyl)-3,5-           N    3.04 3.01                               pyridinedicarboxylate                                                20 oo    Diethyl 2-(difluoromethyl)-                                                                   C.sub.17 H.sub.20 F.sub.5 N.sub.1 O.sub.4                                                  1.4443                                                                            C    51.39                                                                              51.43                              4- -n-butyl-6-(trifluoromethyl)- H    5.07 5.17                               3,5-pyridinedicarboxylate        N    3.53 3.48                      21 uu    Diethyl 2-(difluoromethyl)-4-                                                                 C.sub.19 H.sub.22 F.sub.5 N.sub.1 O.sub.4                                                  1.4614                                                                            C    53.90                                                                              54.19                              cyclohexyl-6-(trifluoromethyl)-  H    5.24 5.33                               3,5-pyridinedicarboxylate        N    3.31 3.51                      22 aaa   Diethyl 2-(difluoromethyl)-4-                                                                 C.sub.18 H.sub.22 F.sub.5 N.sub.1 O.sub.4                                                  1.4489                                                                            C    52.55                                                                              52.29                              (1-ethylpropyl)-6-(trifluoro-    H    5.39 5.43                               methyl)-3,5-pyridinedicarboxylate                                                                              N    3.40 3.33                      23 zz    Diethyl 2-(difluoromethyl)-                                                                   C.sub.16 H.sub.18 F.sub.5 N.sub.1 O.sub.4                                     S.sub.1      1.4709                                                                            C    46.26                                                                              46.40                              4-(methylthioethyl)-6-(tri-      H    4.37 4.41                               fluoromethyl)-3,5-pyridine-      N    3.37 3.42                               dicarboxylate                                                        24 ww    Diethyl 2-(difluoromethyl)-                                                                   C.sub.15 H.sub.16 F.sub.5 N.sub.1 O.sub.5                                                  1.448                                                                             C    46.76                                                                              46.83                              4-(methoxymethyl)-6-(tri-        H    4.19 4.21                               fluoromethyl)-3,5-pyridine-      N    3.68 3.88                               dicarboxylate                                                        25 yy    Diethyl 2-(difluoromethyl)-                                                                   C.sub.15 H.sub.16 F.sub.5 N.sub.1 O.sub.4                                     S.sub.1      1.4748                                                                            C    44.89                                                                              45.04                              4-(methylthiomethyl)-6-(tri-     H    4.02 4.07                               fluoromethyl-3,5-pyridine-       N    3.49 3.35                               dicarboxylate                                                        26 eee   Diethyl 2-(difluoromethyl)-                                                                   C.sub.17 H.sub.20 F.sub.5 N.sub.1 O.sub.4                                                  1.4471                                                                            C    51.39                                                                              51.32                              4-(1-methylpropyl)-6-            H    5.07 5.08                               (trifluoromethyl)-3,5-           N    3.53 3.50                               pyridinedicarboxylate                                                __________________________________________________________________________

EXAMPLE 27 Preparation of diethyl2-(difluoromethyl)-4-(2,2-dimethylpropyl)-6-(trifluoromethyl)-3,5-pyridinedicarboxylate

To a solution of 11.0 g (0.105 mole) of 3, 3-dimethylbutanol in 20 ml ofmethylene chloride is added 3.11 g (0.15 mole) of pyridiniumchlorochromate. The mixture is stirred for 2 hours. The methylenechloride solution is decanted and filtered through a silica gel column.The silica gel column is washed with 200 ml of methylene chloride. Thecombined methylene chloride solution is concentrated at reduced pressureat 20° C. to give 3.7 g of a residue which is 66% pure2,2-dimethylbutyraldehyde.

A mixture of the above aldehyde, 14 g (0.076 mole) of ethyltrifluoroacetoacetate, 0.5 ml of piperidine, and 50 ml of THF is held atreflux for 3 days and cooled to room temperature. To the above THFsolution is passed 36 g of ammonia in one hour. The reaction mixture isstirred with 100 ml of water and 100 ml of ether. The ether layer isseparated, dried, and concentrated to give 14.9 g of a residue. Theresidue is poured into a cold (10° C.) mixture of 50 ml concentratedsulfuric acid and 50 ml of methylene chloride. The mixture is stirredfor 10 minutes and poured onto 300 g of crushed ice. The methylenechloride layer is separated, dried, and concentrated. The residue iskugelrohr distilled at 0.4 torr. The earlier fraction (pot temperature90° C.) is discarded. The second fraction (pot temperature 120° C.) is5.3 g of an oil which is purified by HPLC using 10% ethylacetate/cyclohexane as eluent. The first fraction is 4.83 g of a syrupidentified as diethyl2,6-bis-(trifluoromethyl)-1,4-dihydro-4-(2,2-dimethylpropyl)-3,5-pyridinedicarboxylate.A mixture of 3.83 g (0.0089 mole) of the above syrup, 1.41 g (0.0089mole) of DBU and 50 ml of THF is held at reflux for 20 hours andconcentrated. The residue is stirred with 100 ml of 6 N HCl and 100 mlof ether and filtered. The ether filtrate is separated, washedsuccessively with water, saturated sodium bicarbonate, saturated sodiumchloride, dried, and concentrated. The residue is kugelrohr distilled at1 torr (pot temperature 130° C.) to give 1.9 g of an oil which ispurified by HPLC using 3% ethyl acetate/chloride as eluent. The earlierfraction is discarded. The second fraction affords 1.4 g of the desiredproduct, n_(D) ²⁵ 1.4522.

Anal. Calc'd. for C₁₈ H₂₂ F₅ N₁ O₄ : C, 52.55; H, 5.39; N, 3.40; Found:C, 52.54; H, 5.42; N, 3.40.

The mono-acid compounds, represented by the Formula III, are prepared byselective hydrolysis of diester compounds of Formula II as illustratedby the following examples of 28-37:

EXAMPLE 28 Preparation of2-(difluoromethyl)-4-ethyl-6-(trifluoromethyl)-3,5-pyridinedicarboxvlicacid, 5-ethyl ester

A mixture of 18.5 g (0.050 mole) of the product of Example 12, 3.3 g(0.072 mole) of 85% potassium hydroxide, and 100 ml of ethanol isstirred for 18 hours and poured into water. The reaction mixture isextracted with 200 ml of ether. The aqueous layer is acidified with 50ml of concentrated hydrochloric acid. The oily precipitate is extractedinto ether (2×100 ml) and the ether extracts dried (MgSO₄) andconcentrated. The residual solid is recrystallized from ether-petroleumether to give 14.4 g (84.7%) of the desired product, m.p. 117°-120° C.

Anal. Calc'd. for C₁₃ H₁₂ F₅ N₁ O₄ : C, 45.76; H, 3.54; N, 4.10; Found:C, 45.77; H, 3.42; N, 4.09.

EXAMPLE 29 Preparation of2-(difluoromethyl)-4-propyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylicacid, 5-ethyl ester

A 500 ml flask is charged with 32 g (0.035 mole) of the product ofExample 13 and 150 ml of ethanol. In a separate flask, 5.51 g (0.0835mole) of 85% potassium hydroxide and 75 ml of water are combined. Theaqueous KOH is poured into the 500 ml flask and the mixture heated toreflux for 18 hours. The reaction mixture is concentrated and stirred inwater. The aqueous solution is acidified with concentrated HCl andextracted with ethyl ether. The organics are dried over anhydrous MgSO₄,filtered, and concentrated to yield 23.15 g (78%) of the desired productm.p. 98°-100° C.

Anal. Calc'd. for C₁₄ H₁₄ O₄ N₁ F₅ : C, 47.32; H, 3.98; N, 3.94; Found:C, 47.45; H, 3.99; N, 3.95.

EXAMPLE 30 Preparation of2-(difluoromethyl)-4-iso-butyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylicacid, 5-methyl ester

A mixture of 6.4 g (0.0173 mole) of the product of Example 14, 1.2 g(0.0182 mole) of 85% KOH, 30 ml of methanol, and 2 ml of water isstirred for 2 days and concentrated. The residue was stirred with 200 mlof water and extracted with ether. The aqueous layer is made acidic withconcentrated HCl and the oily precipitate is extracted into ether (2×100ml). The ether extracts are dried and concentrated to give 5.9 g ofsolid which is recrystallized from hexane to give 4.9 g of the desiredproduct as solid, m.p. 100°-102° C.

Anal. Calc'd. for C₁₄ H₁₄ F₅ N₁ O₄ : C, 47.33; H, 3.97; N, 3.94; Found:C, 47.40; H, 3.97; N, 3.90.

In a manner similar to Examples 28, 29, and 30, other2-(difluoromethyl)-6-(trifluoromethyl)-3, 5-pyridinedicarboxylic acid5-ethyl esters of this invention are prepared as indicated in Table 6 byhydrolysis of the listed starting material.

                                      TABLE 6                                     __________________________________________________________________________    3, 5-PYRIDINEDICARBOXYLIC ACID, 5-MONOESTERS                                  Ex.          Starting                                                                           Empirical                                                                              m.p.      Analysis                                 No.                                                                              Product   Material                                                                           Formula  °C.                                                                          n.sub.D.sup.25                                                                    Element                                                                            Calc'd %                                                                           Found %                        __________________________________________________________________________    31 2-(difluoromethyl)-                                                                     Ex. 15                                                                             C.sub.14 H.sub.14 F.sub.5 N.sub.1 O.sub.4                                              80-87     C    47.33                                                                              47.56                             4-isopropyl-6-(tri-               H    3.97 4.19                              fluoromethyl)-3,5-                N    3.94 3.62                              pyridinedicarboxylic                                                          acid, 5-ethyl ester                                                        32 2-(difluoromethyl)-                                                                     Ex. 16                                                                             C.sub.15 H.sub.16 F.sub.5 N.sub.1 O.sub.4                                                    1.4453                                                                            C    48.79                                                                              48.55                             4-isobutyl-6-(tri-                H    4.37 4.51                              fluoromethyl)-3,5-                N    3.79 3.66                              pyridinedicarboxylic                                                          acid, 5-ethyl ester                                                        33 2-(difluoromethyl)-                                                                     Ex. 20                                                                             C.sub.15 H.sub.16 F.sub.5 N.sub.1 O.sub.4                                              83-85     C    48.79                                                                              48.86                             4- -n-butyl-6-(tri-               H    4.37 4.36                              fluoromethyl)-3,5-                N    3.79 3.71                              pyridinedicarboxylic                                                          acid, 5-ethyl ester                                                        34 2-(difluoromethyl)-                                                                     Ex. 17                                                                             C.sub.14 H.sub.12 F.sub.5 N.sub.1 O.sub.4                                              113-115   C    47.60                                                                              47.67                             4-cyclopropyl-6-(tri-             H    3.42 3.56                              fluoromethyl)-3,5-                N    3.97 3.92                              pyridinedicarboxylic                                                          acid, 5-ethyl ester                                                        35 2-(difluoromethyl)-                                                                     Ex. 23                                                                             C.sub.14 H.sub.14 F.sub.5 N.sub.1 O.sub.4 S.sub.1                                      121.5-122.5                                                                             C    43.41                                                                              43.51                             4-(methylthioethyl)-              H    3.64 3.69                              6-(trifluoromethyl)-              N    3.62 3.62                              3,5-pyridinedi-                                                               carboxylic acid,                                                              5-ethyl ester                                                              36 2-(difluoromethyl)-                                                                     Ex. 24                                                                             C.sub.13 H.sub.12 F.sub.5 N.sub.1 O.sub.5                                                108-108.5                                                                             C    43.71                                                                              43.68                             4-(methoxymethyl)-                H    3.39 3.45                              6-(trifluoromethyl)-              N    3.92 3.88                              3,5-pyridinedi-                                                               carboxylic acid,                                                              5-ethyl ester                                                              37 2-(difluoromethyl)-                                                                     Ex. 21                                                                             C.sub.17 H.sub.18 F.sub.5 N.sub.1 O.sub.4                                              88-91     C    51.65                                                                              51.45                             4-cyclohexyl-6-                   H    4.59 4.58                              (trifluoromethyl)-                N    3.54 3.60                              3,5-pyridinedi-                                                               carboxylic acid,                                                              5-ethyl ester                                                              __________________________________________________________________________

The pyridinedicarboxylic acids of Formula V in this invention areprepared by complete hydrolysis of compounds of Formula (D) and II asillustrated by the following examples of 38-43.

EXAMPLE 38 Preparation of2,6-bis(trifluoromethyl)-4-ethyl-3,5-pyridinedicarboxylic acid

A single-necked flask is charged with 10 g (0.025 mole) of the productof Example 1 and 100 ml of 10% aqueous KOH. The mixture is refluxed for48 hours and the aqueous mixture is extracted once with ethyl ether. Thewater layer is acidified with concentrated HCl and the organics areextracted twice with ether, dried over MgSO₄, and concentrated to give2.73 g (32.23%) of the desired product, m.p. 263°-269° C. (decomp.).

Anal. Calc'd. for C₁₁ H₇ O₄ N₁ F₆ : C, 39.87; H, 2.11; N, 4.22; F,34.44; Found: C, 39.92; H, 2.22; N, 4.17; F, 34.60.

EXAMPLE 39 Preparation of2-idifluoromethyl)-4-n-propyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylicacid

A mixture of 20.1 g (0.0525 mole) of the product of Example 13, 11.4 gof 85% KOH, and 100 ml of methanol is held at reflux for 19 hours andconcentrated. The residue is treated with 200 ml of water and extractedwith ether. The aqueous layer is separated and acidified with 30 ml ofconcentrated HCl. The oily precipitate is extracted into ether and theether extract is dried and concentrated. The residue is recrystallizedfrom chloroform to give 4.2 g (24%) of the desired product, m.p.235.5°-236.5° C.

Anal. Calc'd. for C₁₂ H₁₀ F₅ NO₄ : C, 44.05; H, 3.08; N, 4.28; Found C,43.92; H, 2.98; N, 4.19.

The combined mother liquor is concentrated and the residue treated with10 g of KOH, 50 ml of methanol, and 2 ml of water as described above togive an additional 2.2 g (12.8%) of the desired product.

EXAMPLE 40

Preparation of6-(difluoromethyl)-4-ethyl-2-(trifluoromethyl)-3,5-pyridinedicarboxylicacid

A 1-liter flask is charged with 60 g (0.163 mole) of the product ofExample 12 and 200 ml of methyl alcohol. In another flask, 150 ml ofwater and 21.52 g (0.326 mole) of potassium hydroxide are combined. Theaqueous KOH is poured into the 1-liter flask and the mixture is heatedto reflux overnight. The reaction mixture is cooled and extracted oncewith ethyl ether. The aqueous layer is acidified with concentratedhydrochloric acid and extracted with ethyl ether. The organics are driedon anhydrous magnesium sulfate, filtered, and concentrated to yield26.72 g (52%) of the desired product, m.p. 237°-239° C.

Anal. Calc'd. for C₁₁ H₈ O₄ N₁ F₅ : C, 42.17; H, 2.55; N, 4.47; Found:C, 43.29; H, 2.81; N, 4.34.

In a manner similar to Examples 39 and 40, other unsymmetricalpyridinedicarboxylic acids of this invention are prepared as indicatedin Table 7 utilizing the starting material listed in Table 7.

                                      TABLE 7                                     __________________________________________________________________________    Ex.          Starting                                                                           Empirical                                                                              m.p.      Analysis                                 No.                                                                              Product   Material                                                                           Formula  °C.                                                                          n.sub.D.sup.25                                                                    Element                                                                            Calc'd %                                                                           Found %                        __________________________________________________________________________    41 2-(difluoromethyl)-                                                                     Ex. 15                                                                             C.sub.12 H.sub.10 F.sub.5 N.sub.1 O.sub.4                                              278 (dec) C    44.05                                                                              43.99                             4-isopropyl-6-(tri-               H    3.08 3.10                              fluoromethyl)-3,5-                N    4.28 4.24                              pyridinedicarboxylic                                                          acid                                                                       42 2-(difluoromethyl)-                                                                     Ex. 24                                                                             C.sub.11 H.sub.8 F.sub.5 N.sub.1 O.sub.5                                               243-247   C    40.14                                                                              39.95                             4-methoxymethyl-6-                H    2.45 2.66                              (trifluoromethyl)-                N    4.26 4.22                              3,5-pyridinedi-                                                               carboxylic acid                                                            43 2-(difluoromethyl)-                                                                     Ex. 14                                                                             C.sub.13 H.sub.12 F.sub.5 N.sub.1 O.sub.4                                                219-219.5                                                                             C    45.76                                                                              45.66                             4-isobutyl-6-(tri-                H    3.54 3.57                              fluoromethyl)-3,5-                N    4.10 4.08                              pyridinedicarboxylic                                                          acid                                                                       __________________________________________________________________________

The mono acid chlorides and diacid chlorides in this inventionrepresented by the Formula IV and VI are prepared from the correspondingmono acids and diacids as illustrated by the following Examples 44-51:

EXAMPLE 44 Preparation of ethyl5-chlorocarbonyl-6-(di-fluoromethyl)-4-isopropyl-2-(trifluoromethyl)-pyridine-3-carboxylate

A mixture of 3.72 g (0.105 mole) of the product of Example 31 and 50 mlof thionyl chloride is held at reflux for 18 hours and concentrated invacuo to give 3.8 g (97%) of the desired product as an oil, n_(D) ²⁵1.4570.

Anal. Calc'd. for C₁₄ H₁₃ Cl₁ F₅ NO₃ : C, 45.00; H, 3.51; N, 3.75;Found: 45.10; H, 3.53; N, 3.68.

In a manner similar to Example 44, other monoacid chlorides and diacidchlorides of this invention are prepared from the indicated startingmaterials and listed in Table 8.

                                      TABLE 8                                     __________________________________________________________________________    Ex.           Starting                                                                           Empirical m.p.    Analysis                                 No.                                                                              Product    Material                                                                           Formula   °C.                                                                        n.sub.D.sup.25                                                                    Element                                                                            Calc'd %                                                                           Found %                        __________________________________________________________________________    45 6-(difluoromethyl)-4-                                                                    Ex. 40                                                                             C.sub.11 H.sub.6 O.sub.2 N.sub.1 F.sub.5 Cl.sub.2                                           1.4706                                                                            C    37.74                                                                              37.83                             ethyl-2-(trifluoro-               H    1.73 2.12                              methyl)-3,5-pyridine-             N    4.00 3.70                              dicarboxylic diacid                                                           chloride                                                                   46 ethyl 5-chloro-                                                                          Ex. 28                                                                             C.sub.13 H.sub.11 O.sub.3 N.sub.1 F.sub.5 Cl                                                1.4583                                                                            C    43.45                                                                              43.60                             carbonyl-6-(difluoro-             H    3.06 3.09                              methyl)-4-ethyl-2-                N    3.89 3.91                              (trifluoromethyl)-3-                                                          pyridinecarboxylate                                                        47 ethyl 5-chloro-                                                                          Ex. 29                                                                             C.sub.14 H.sub.13 O.sub.3 N.sub.1 F.sub.5 Cl                                            33-34   C    44.99                                                                              45.02                             carbonyl-6-(difuoro-              H    3.48 3.52                              methyl)-4-propyl-2-               N    3.74 3.71                              (trifluoromethyl)-3-                                                          pyridinecarboxylate                                                        48 2,6-bis(trifluoro-                                                                       Ex. 38                                                                             C.sub. 11 H.sub.5 O.sub.2 N.sub.1 F.sub.6 Cl.sub.2                                          1.4509                                                                            C    35.90                                                                              36.05                             methyl)-4-ethyl-3,5-              H    1.37 1.43                              pyridinedicarboxylic              N    3.81 3.73                              acid diacid chloride                                                       49 ethyl 5-(chloro-                                                                         Ex. 33                                                                             C.sub.15 H.sub.15 Cl.sub.1 F.sub.5 N.sub.1 O.sub.3                                      46-48   C    46.47                                                                              46.33                             carbonyl)-4- -n-butyl-            H    3.90 3.78                              6-(difluoromethyl)-               N    3.61 3.58                              2-(trifluoromethyl)-                                                          3-pyridinecarboxylate                                                      50 ethyl 5-(chloro-                                                                         Ex. 34                                                                             C.sub.14 H.sub.11 Cl.sub.1 F.sub.5 N.sub.1 O.sub.3                                      53-54   C    45.24                                                                              45.24                             carbonyl)-4-cyclo-                H    2.98 3.01                              propyl-6-(difluoro-               N    3.77 3.78                              methyl)-2-(trifluoro-                                                         methyl)-3-pyridine-                                                           carboxylate                                                                51 2-(difluoromethyl)-                                                                      Ex. 39                                                                             C.sub.12 H.sub.8 O.sub.2 N.sub.1 F.sub.5 Cl.sub.2                                           1.4713                                                                            C    39.58                                                                              39.61                             4-propyl-6-(tri-                  H    2.21 2.34                              fluoromethyl)-3,5-                N    3.85 3.50                              pyridinedicarboxylic                                                          acid diacid chloride                                                       __________________________________________________________________________

EXAMPLE 52 Preparation of 3-ethyl 5-methyl6-(difluoromethyl)-4-propyl-2-(trifluoromethyl)-3,5-pyridinedicarboxylate

A mixture of 5.0 g of the product of Example 47 and 100 ml of methanolis held at reflux for 18 hours and concentrated. The residue isdissolved in ether. The ether solution is washed with aqueous saturatedsodium bicarbonate, dried, and concentrated to give 2.37 g (48%) of thedesired product as an oil, n_(D) ²⁵ 1.4428.

Anal. Calc'd. for C₁₅ H₁₆ F₅ N₁ O₄ : C, 48.92; H, 4.11; N, 3.80; Found:C, 49.00; H, 4.13; N, 3.76.

EXAMPLE 53 Preparation of 3-ethyl 5-methyl6-(difluoromethyl)-4-isopropyl-2-(trifluoromethyl)-3,5-pyridinedicarboxylate

A mixture of 2.8 g (0.0074 mole) of the product of Example 44 and 60 mlof methanol is held at reflux for 3 hours and concentrated to give 1.61g (59%) of the desired product as an oil, n_(D) ²⁵ 1.4483.

Anal Calc'd. for C₁₅ H₁₆ F₅ N₁ O₄ : C, 48.79; H, 4.37; N, 3.79; Found:C, 48.69; H, 4.41; N, 3.75.

EXAMPLE 54 Preparation of 3-ethyl 5-ethyl2-(difluoromethyl)-4-isobutyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylat

A mixture of 10 g (0.0270 mole) of the product of Example 32 and 100 mlof thionyl chloride is held at reflux overnight and concentrated to givea residue (9.59 g). A portion (5.03 g) of this residue is held at refluxwith 50 ml of methanol for 3 hours and concentrated. The residue (3.72g) is kugelrohr distilled to give 2.83 g (56.3%) of the desired productas an oil, n_(D) ²⁵ 1.4453.

Anal Calc'd. for C₁₆ H₁₈ F₅ N₁ O₄ : C, 50.13; H, 4.73; N, 3.65; Found:C, 49.91; H, 4.87; N, 3.43.

EXAMPLE 55 Preparation of 3-ethyl 5-methyl4-cyclopropyl-6-(difluoromethyl)-2-(trifluoromethyl)-3,5-pyridinedicarboxylate

A mixture of 3.0 g (0.008 mole) of the product of Example 50 and 30 mlof methanol is held at reflux for 1.5 hours and concentrated. Theresidue (2.81 g) is recrystallized from petroleum ether to give 1.85 g(63.1%) of the desired product as a white solid, m.p. 61°-63° C.

Anal. Calc'd. for C₁₅ H₁₄ F₅ N₁ O₄ : C, 49.05; H, 3.84; N, 3.81; Found:C, 48.99; H, 3.88; N, 3.79.

A second crop (0.69 g, 23.5%) is also isolated from the mother liquor,m.p. 49°-52° C.

EXAMPLE 56 Preparation ofdimethyl-2,6-bis(trifluoromethyl)-4-ethyl-3,5-pyridinedicarboxylate

To 70 ml of methanol in a 500 ml flask is added 5 g (0.0136 mole) ofproduct of Example 48. The reaction mixture is heated to reflux andrefluxed for 9 hours. The mixture is concentrated, diluted with ethylether, washed with aqueous saturated sodium bicarbonate solution, driedin anhydrous MgSO₄, and concentrated to yield 3.3 g (68%) of the desiredproduct, m.p. 45°-47° C.

Anal. Calc'd. for C₁₃ H₁₁ O₄ N₁ F₆ : C, 43.45; H, 3.06: N, 3.89; Found:C, 43.57; H, 3.06; N, 3.86.

In a manner similar to the procedure of Examples 52-56 above, othernovel compounds of this invention are prepared. As noted above withrespect to Table 4, having due regard for the starting materialsubstituted and reaction conditions, suitable to the reactants employed,additional examples are provided as noted in Table 9 below.

                                      TABLE 9                                     __________________________________________________________________________    MIXED ESTERS OF 3, 5-PYRIDINEDICARBOXYLIC ACIDS                               Ex.                                                                              Starting             Empirical                                                                              m.p.    Analysis                             No.                                                                              Material                                                                           Reactant                                                                           Product    Formula  °C.                                                                        n.sub.D.sup.25                                                                    Element                                                                            Calc'd %                                                                           Found                      __________________________________________________________________________                                                       %                          57 Ex. 46                                                                             iso- 5-ethyl 3-iso-                                                                           C.sub.16 H.sub.18 O.sub.4 N.sub.1 F.sub.5                                                  1.4440                                                                            C    50.13                                                                              50.21                              propanol                                                                           propyl-2-(diluoro-          H    4.69 4.72                                    methyl)-4-ethyl-6-          N    3.65 3.66                                    (trifluoromethyl)-                                                            3,5-pyridinedi-                                                               carboxylate                                                      58 Ex. 45                                                                             butanol                                                                            dibutyl 6-(di-                                                                           C.sub.19 H.sub.24 O.sub.4 N.sub.1 F.sub.5                                                  1.4467                                                                            C    53.65                                                                              53.05                                   fluoromethyl)-4-            H    5.69 5.55                                    ethyl-2-(tri-               N    3.29 3.37                                    fluoromethyl)-                                                                3,5-pyridine-                                                                 dicarboxylate                                                    59 Ex. 45                                                                             methanol                                                                           dimethyl 2-(di-                                                                          C.sub.13 H.sub.12 O.sub.4 N.sub.1 F.sub.5                                              47-49   C    45.74                                                                              45.79                                   fluoromethyl)-4-            H    3.51 3.57                                    ethyl-6-(tri-               N    4.10 4.07                                    fluoromethyl)-                                                                3,5-pyridinedi-                                                               carboxylate                                                      60 Ex. 48                                                                             iso- bis(isopropyl)                                                                           C.sub.17 H.sub.19 O.sub.4 N.sub.1 F.sub.6                                              46-49   C    49.15                                                                              49.21                              propanol                                                                           2,6-bis(trifluoro-          H    4.57 4.63                                    methyl)-4-ethyl-            N    3.37 3.37                                    3,5-pyridinedi-                                                               carboxylate                                                      61 Ex. 46                                                                             allyl                                                                              3-ethyl 5-(2-                                                                            C.sub.16 H.sub.16 O.sub.4 N.sub.1 F.sub.5                                                  1.4525                                                                            C    50.39                                                                              50.34                              alcohol                                                                            propenyl) 6-di-             H    4.19 4.22                                    fluoromethyl)-4-            N    3.67 3.66                                    ethyl-2-(trifluoro-                                                           methyl)-3,5-                                                                  pyridinedicarboxylate                                            62 Ex. 46                                                                             2-chloro                                                                           5-ethyl 3-(2-                                                                            C.sub.15 H.sub.15 O.sub.4 N.sub.1 F.sub.5                                     Cl.sub.1     1.4570                                                                            C    44.62                                                                              44.48                              ethanol                                                                            chloroethyl) 2-             H    3.71 3.76                                    (difluoromethyl)-           N    3.47 3.40                                    4-ethyl-6-(trifluoro-                                                         methyl)-3,5-                                                                  pyridinedicarboxylate                                            63 Ex. 46                                                                             methyl                                                                             3-ethyl 5-methyl                                                                         C.sub.14 H.sub.14 O.sub.4 N.sub.1 F.sub.5                                                  1.4448                                                                            C    47.32                                                                              47.23                              alcohol                                                                            6-(difluoromethyl)-         H    3.94 3.99                                    4-ethYl-2-(trifluoro-       N    3.94 3.92                                    methyl)-3,5-                                                                  pyridinedicarboxylate                                            64 Ex. 46                                                                             2-fluoro                                                                           3-ethyl 5-(2-                                                                            C.sub.15 H.sub.15 F.sub.6 N.sub.1 O.sub.4                                                  1.4459                                                                            C    46.52                                                                              46.76                              ethanol                                                                            fluoroethyl) 6-(di-         H    3.90 4.20                                    fluoromethyl)-4-            N    3.62 3.64                                    ethyl-2-(trifluoro-                                                           methyl)-3,5-pyridine-                                                         dicarboxylate                                                    65 Ex. 49                                                                             methanol                                                                           3-ethyl 5-methyl-                                                                        C.sub.16 H.sub.18 F.sub.5 N.sub.1 O.sub.4                                                  1.4465                                                                            C    50.13                                                                              49.97                                   4- -n-butyl-6-(di-          H    4.73 4.77                                    fluoromethyl)-2-            N    3.65 3.64                                    (trifluoromethyl)-                                                            3,5-pyridinedi-                                                               carboxylate                                                      66 Ex. 49                                                                             2,2,2-                                                                             3-ethyl 5-(2,2,2-                                                                        C.sub.17 H.sub.17 F.sub.8 N.sub.1 O.sub.4                                              37-38   C    45.24                                                                              45.69                              tri- trifluoroethyl)-            H    3.80 3.86                               fluoro-                                                                            4- -n-butyl-6-(di-          N    3.10 3.14                               ethanol                                                                            fluoromethyl)-                                                                3,5-pyridinedi-                                                               carboxylate                                                      67 Ex. 51                                                                             methanol                                                                           dimethyl 2-(di-                                                                          C.sub.14 H.sub.14 F.sub.5 N.sub.1 O.sub.4                                                  1.4435                                                                            C    52.55                                                                              52.59                                   fluoromethyl)-4-            H    5.39 5.28                                     -n-propyl-6-(tri-          N    3.40 3.37                                    fluoromethyl)-                                                                3,5-pyridinedi-                                                               carboxylate                                                      68 Ex. 51                                                                              -n- dipropyl 2-(di-                                                                          C.sub.18 H.sub.22 F.sub.5 N.sub.1 O.sub.4                                                  1.4451                                                                            C    52.55                                                                              52.59                              propanol                                                                           fluoromethyl)-4-            H    5.39 5.28                                     -n-propyl-6-(tri-          N    3.40 3.37                                    fluoromethyl)-                                                                3,5-pyridinedi-                                                               carboxylate                                                      __________________________________________________________________________

EXAMPLE 69 Preparation of 3-ethyl 5-methyl2-(difluoromethyl)-4-isobutyl-6-(trifluoromethyl)-3,5-pyridinecarboxylate

A mixture of 2.9 g (0.00817 mole) of the product of Example 30, 11 g(0.0705 mole) of ethyl iodide, 1.3 g (0.00942 mole) of potassiumcarbonate, and 50 ml of acetone is held at reflux for 4 hours andconcentrated. The residue is treated with 200 ml of water and extractedwith 50 ml of ether twice. The ether extracts are washed once with 50 mlof sodium bicarbonate, dried (MgSO₄), and concentrated to give an oilwhich is kugelrohr distilled at 2 torr (pot temperature 130° C.) to give3.0 g (98%) of the desired product as a liquid, n_(D) ²⁵ 14469.

Anal. Calc'd. for C₁₆ H₁₈ F₅ N₁ O₄ : C, 50.13; H, 4.73; N, 3.65; Found:C, 50.19; H, 4.78; N, 3.56.

In a manner similar to the procedure of Example 69, otherpyridinedicarboxylates of this invention are prepared. As noted abovewith respect to Table 4, having due regard for the starting materialsubstituted and reaction conditions suitable to the reactants employed,additional examples are provided as noted in Table 10.

                                      Table 10                                    __________________________________________________________________________    ALTERNATIVE PREPARATION OF                                                    PYRIDINEDICARBOXYLATE DERIVATIVES                                             __________________________________________________________________________    Ex.                                                                              Starting      Solvent-                                                     No.                                                                              Material                                                                            Reactant                                                                              Condition                                                                             Product                                              __________________________________________________________________________    70 Ex. 35                                                                              KF-CH.sub.3 I                                                                         DMF - room                                                                            3-ethyl 5-methyl                                                      temperature                                                                           6-(difluoromethyl)-                                                           4-(methylthioethyl)-                                                          2-(trifluoromethyl)-                                                          3,5-pyridinedi-                                                               carboxylate                                          71 Ex. 36                                                                              KF-CH.sub.3 I                                                                         DMF - room                                                                            3-ethyl 5-methyl                                                      temperature                                                                           6-(difluoromethyl)-                                                           4-(methoxymethyl)-                                                            2-(trifluoromethyl)-                                                          3,5-pyridinedi-                                                               carboxylate                                          72 Ex. 41                                                                              K.sub.2 CO.sub.3 -                                                                    acetone -                                                                             dimethyl 2-(di-                                               CH.sub.3 I                                                                            reflux  fluoromethyl)-4-iso-                                                          propyl-6-(trifluoro-                                                          methyl)-3,5-pyridine-                                                         dicarboxylate                                        73 Ex. 43                                                                              K.sub.2 CO.sub.3 -                                                                    DMF - room                                                                            dipropargyl 2-(di                                             BrCH.sub.2 C.tbd.CH                                                                   Temperature                                                                           fluoromethyl)-4-iso-                                                          butyl-6-(trifluoro-                                                           methyl)-3,5-(pyridine-                                                        dicarboxylate                                        74 Ex. 42                                                                              K.sub.2 CO.sub.3 -                                                                    acetone -                                                                             dimethyl 2-(di-                                               CH.sub.3 I                                                                            reflux  fluoromethyl)-4-                                                              (methoxymethyl)-                                                              6-(trifluoromethyl)-                                                          3,5-pyridinedi-                                                               carboxylate                                          __________________________________________________________________________    Exp.                                                                              Empirical m.p.    Analysis                                                No. Formula   °C.                                                                        n.sub.D.sup.25                                                                    Element                                                                            Calc'd %                                                                           Found %                                       __________________________________________________________________________    70  C.sub.15 H.sub.16 F.sub.5 N.sub.1 O.sub.4 S.sub.1                                       59-60.5 C    44.89                                                                              44.87                                                               H    4.02 4.02                                                                N    3.49 3.47                                          71  C.sub.14 H.sub.14 F.sub.5 NO.sub.5                                                      52-54   C    45.29                                                                              45.08                                                               H    3.80 3.79                                                                N    3.77 3.69                                          72  C.sub.14 H.sub.14 F.sub.5 N.sub.1 O.sub.4                                                   1.4573                                                                            C    47.33                                                                              47.46                                                               H    3.97 4.03                                                                N    3.94 3.88                                          73  C.sub.19 H.sub.16 F.sub.5 N.sub.1 O.sub.4                                                   1.4696                                                                            C    54.68                                                                              54.61                                                               H    3.86 3.84                                                                N    3.36 3.34                                          74  C.sub.13 H.sub.12 F.sub.5 N.sub.1 O.sub.5                                               43-44   C    43.71                                                                              43.78                                                               H    3.39 3.40                                                                N    3.92 3.89                                          __________________________________________________________________________

EXAMPLE 75 Preparation of 3-methyl 5-ethyl2-(difluoromethyl)-4-(1-ethylpropyl)-6-(trifluoromethyl)-3,5-pyridinedicarboxylate

A 12.0 g (0.0386 mole) of a 90% pure product of Example 22, 2.6 g(0.0394 mole) of 85% potassium hydroxide, 30 ml of ethanol, and 2 ml ofwater is held at reflux for 20 hours and concentrated. The residue istreated with 100 ml of water and extracted with 100 ml of ether. Theaqueous layer is acidified with 50 ml of concentrated HCl. The oilprecipitate is extracted with 200 ml of ether. The ether solution isdried (MgSO₄) and concentrated to give 10.8 g of a syrup. Part (8.8 g)of this syrup is mixed with 34 g of methyl iodide, 3.16 g (0.0230 mole)of K₂ CO₃ and 30 ml of acetone. The mixture was stirred and held atreflux for 3 hours and concentrated. The residue is stirred with 100 mlof ether and 100 ml of water. The ether solution is washed once with 50ml of saturated NaHCO₃, dried (MgSO₄), and concentrated to give 7.6 g ofa brown oil which is kugelrohr distilled at 1.5 torr (pot temperature of115° C.) to give 7.6 g distillate. This distillate is chromatographed onsilica gel by HPLC using 3% ethyl acetate-cyclohexane as eluent. Thefirst fraction (retention time 14-16 minutes) is 2.0 g of a mixture ofthe desired product and unidentified material. The second fraction(retention time 16-22 minutes) is 4.3 g of an oil which after kugelrohrdistillation at 1 torr (pot temperature of 130° C.) gives 4.1 g ofdesired product as a colorless oil, n_(D) ²⁵ 1.4519.

Anal. Calc'd. for C₁₇ H₂₀ F₅ NO₄ : C, 51.39; H, 5.07; N, 3.53; Found: C,51.40; H, 5.14; N, 3.50.

Other pyridinedicarboxylic acid monoesters in this invention listed inTable 11 are prepared by a method similar to that described for Example30.

                                      TABLE 11                                    __________________________________________________________________________    PYRIDINEDICARBOXYLIC ACID MONOESTERS                                          Ex.          Starting                                                                           Empirical    Anaylsis %                                     No.                                                                              Compound  Material                                                                           Formula M.P. Element                                                                            Calc'd                                                                            Found                                 __________________________________________________________________________    76 2-(difluoromethyl)-                                                                     Ex. 68                                                                             C.sub.15 H.sub.16 F.sub.5 NO.sub.4                                                    69-71                                                                              C    48.79                                                                             48.71                                    4-n-propyl-6-               H    4.37                                                                              4.40                                     (trifluoromethyl)-          N    3.79                                                                              3.79                                     3,5-pyridinedi-                                                               carboxylic acid,                                                              5-n-propyl ester                                                           77 2-(difluoromethyl)-                                                                     Ex. 67                                                                             C.sub.13 H.sub.12 F.sub.5 NO.sub.4                                                    113-115                                                                            C    45.76                                                                             45.86                                    4- -n-propyl-6-             H    3.54                                                                              3.65                                     (trifluoromethyl)-          N    4.10                                                                              3.96                                     3,5-pyridinedi-                                                               carboxylic acid,                                                              5-methyl ester                                                             78 2-(difluoromethyl)-                                                                     Ex. 74                                                                             C.sub.12 H.sub.10 F.sub.5 N.sub.1 O.sub.5                                             132-133.5                                                                          C    41.99                                                                             42.09                                    4-(methoxymethyl)-          H    2.94                                                                              2.95                                     6-(trifluoromethyl)-        N    4.08                                                                              4.03                                     3,5-pyridinedi-                                                               carboxylic acid,                                                              5-methyl ester                                                             79 2-(difluoromethyl)-                                                                     Ex. 73                                                                             C.sub.16 H.sub.14 F.sub.5 N.sub.1 O.sub.4                                             98.5-99.5                                                                          C    50.67                                                                             50.56                                    4-isobutyl-6-               H    3.72                                                                              3.75                                     (trifluoromethyl)-          N    3.69                                                                              3.63                                     3,5-pyridinedi-                                                               carboxylic acid,                                                              5-propargyl ester                                                          __________________________________________________________________________

EXAMPLE 80

Preparation of 3-methyl 5-propargyl2-(difluoromethyl)-4-isobutyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylat

A mixture of 2.1 g of the product of Example 79, 1.1 g of potassiumcarbonate, 25.3 g of methyl iodide, and 40 ml of DMF is stirred for 24hours and poured into water. The mixture is extracted with ether. Theether extract is washed twice with 100 ml of water, dried, andconcentrated. The residue is kugelrohr distilled at 0.5 torr to give 2.1g (96%) of the desired product as an oil, n_(D) ²⁵ 1.4598.

Anal. Calc'd. for C₁₇ H₁₆ F₅ N₁ O₄ : C, 51.91; H, 4.10; N, 3.56; Found:C, 51.92; H, 4.14; N, 3.56.

EXAMPLE 81 Preparation of 3-ethyl 5-methyl2-(difluoromethyl)-4-(methoxymethyl)-6-(trifluoromethyl)-3,5-pyridinedicarboxylate

In accordance with the procedure of Example 69 with the exception thatthe starting material is the product of Example 78, there is obtained3-ethyl5-methyl-2-(difluoromethyl)-4-(methoxymethyl)-6-(trifluoromethyl)-3,5-pyridinedicarboxylateas an oil, n_(D) ²⁵ 1.4467.

Anal. Calc'd. for C₁₄ H₁₄ F₅ N₁ O₅ : C, 45.29; H, 3.80; N, 3.77; Found:C, 45.39; H, 3.84; N, 3.74.

Other 5-chlorocarbonyl-3-pyridinecarboxylates of this invention areprepared from the corresponding 3,5-pyridinedicarboxylic acid3-monoester by a method similar to that described for Example 44 and arelisted in Table 12.

                                      TABLE 12                                    __________________________________________________________________________    Ex.           Starting                                                                           Empirical        Anaylsis %                                No.                                                                              Compound   Material                                                                           Formula  m.p.                                                                              nN.sub.D .sup.25                                                                  Element                                                                            Calc'd                                                                            Found                            __________________________________________________________________________    82 3-methyl 5-chloro-                                                                       Ex. 77                                                                             C.sub.13 H.sub.11 Cl.sub.1 F.sub.5 N.sub.1 O.sub.3                                     47-50   C    43.41                                                                             43.62                               carbonyl-6-(difluoro-            H    3.08                                                                              3.05                                methyl)-4- -n-propyl-2           N    3.89                                                                              3.76                                (trifluoromethyl)-                                                            3-pyridinecarboxylate                                                      83 3-propyl 5-chloro-                                                                       Ex. 76                                                                             C.sub.13 H.sub.15 Cl.sub.1 F.sub.5 N.sub.1 O.sub.3                                         1.4560                                                                            C    46.47                                                                             46.39                               carbonyl-6-(difluoro-            H    3.90                                                                              3.95                                methyl)-4- -n-propyl-            N    3.61                                                                              3.60                                2-(trifluoromethyl)-                                                          3-pyridinecarboxylate                                                      __________________________________________________________________________

Other unsymmetrical pyridinedicarboxylates in this invention areprepared from the corresponding 5-chlorocarbonyl-3-pyridinecarboxylateand an appropriate alcohol by a method similar to that described inExample 52 and are listed in Table 13.

                                      TABLE 13                                    __________________________________________________________________________    Ex.                                                                              Starting               Empirical   Analysis                                No.                                                                              Material                                                                           Reactant                                                                            Product     Formula n.sub.D .sup.25                                                                   Element                                                                            Calc'd %                                                                           Found %                       __________________________________________________________________________    84 Ex. 82                                                                             n-propanol                                                                          3-methyl 5- -n-propyl                                                                     C.sub.16 F.sub.18 F.sub.5 N.sub.1 O.sub.4                                             1.4447                                                                            C    50.13                                                                              50.25                                       6-(difluoromethyl)-     H    4.73 4.73                                        4- -n-propyl-2-(trifluoro-                                                                            N    3.65 3.62                                        methyl)-3,5-pyridinedi-                                                       carboxylate                                                     85 Ex. 83                                                                             methanol                                                                            3-methyl 5- -n-propyl-                                                                    C.sub.16 H.sub.18 F.sub.5 N.sub.1 O.sub.4                                             1.4453                                                                            C    50.13                                                                              50.54                                       2-(difluoromethyl)-     H    4.73 4.71                                        4- -n-propyl-6-(trifluoro-                                                                            N    3.65 3.60                                        methyl-3,5-pyridinedi-                                                        carboxylate                                                     86 Ex. 82                                                                             ethanol                                                                             3-methyl 5-ethyl                                                                          C.sub.15 H.sub.16 F.sub.5 N.sub.1 O.sub.4                                             1.4439                                                                            C    48.79                                                                              48.69                                       6-(difluoromethyl)-     H    4.37 4.44                                        4- -n-propyl-2-(trifluoro-                                                                            N    3.79 3.74                                        methyl)-3,5-pyridinedi-                                                       carboxylate                                                     __________________________________________________________________________

EXAMPLE 87

Preparation of 3-ethyl 5-methyl2,6-bis-(difluoro-methyl)-4-propyl-3,5-pyridinedicarboxylate

A mixture of 5.67 g (0.016 mol) of the product of Example 11, 1.06 g(0.016 mol) of 85% KOH, 40 ml of ethanol, and 10 ml of water is stirredfor 24 hours and concentrated. The residue is treated with 50 ml ofwater and extracted with 50 ml of ether. The aqueous layer is acidifiedwith 50 ml of concentrated HCl. The oil precipitate is extracted withether, dried (MgSO₄), and concentrated to give 2.64 g (49%) of amonoacid. Part (1.64 g, 0.00486 mole) of this acid is refluxed with 10ml of thionyl chloride until HCl evolution ceased. The reaction mixtureis concentrated and the residue is dissolved in ether, dried over MgSO₄,and concentrated to give 1.22 g of the desired product as an oil, n_(D)²⁵ 1.4629.

Anal Calc'd. for C₁₅ H₁₇ F₄ NO₄ : C, 51.29; H, 4.88; N, 3.99; Found: C,50.93; H, 4.99; N, 3.87.

EXAMPLE 88 Preparation of ethyl 5-(aminocarbonyl)6-(difluoromethyl)-4-ethyl-2-(trifluoromethyl) 3-pyridinecarboxylate

An excess of ammonia gas (3 g, 0.176 mole) is condensed into athree-necked 250 ml flask using dry ice acetone condensers. To 50 ml ofether is added 7 g (0.0196 mole) of the product of Example 46. The ethersolution is slowly poured into the reaction flask and the total mixtureis stirred for 18 hours. The resulting solid is washed with water anddried under vacuum for 18 hours to yield 5.67 g (86%) of the desiredproduct, m.p. 165°-167° C.

Anal. Calc'd. for C₁₃ H₁₃ O₃ N₂ F₅ : C, 45.88; H, 3.82; N, 8.23; Found:C, 45.87; H, 3.84; N, 8.23.

In a manner similar to Example 88, other pyridinecarboxamides of thisinvention are prepared as indicated in Table 14.

                                      TABLE 14                                    __________________________________________________________________________    Ex.                                                                              Starting                 Empirical                                                                             m.p. Analysis %                           No.                                                                              Material                                                                           Reactant                                                                             Product      Formula °C.                                                                         Element                                                                            Calc'd                                                                            Found                       __________________________________________________________________________    89 Ex. 46                                                                             butylamine                                                                           ethyl 5-[(butylamino)-                                                                     C.sub.17 H.sub.21 O.sub.3 N.sub.2 F.sub.5                                             83-85                                                                              C    51.51                                                                             51.38                                      carbonyl]-6-(difluoro-    H    5.30                                                                              5.35                                       methyl)-4-ethyl-2-        N    7.07                                                                              7.02                                       (trifluoromethyl)-3-                                                          pyridinecarboxylate                                            90 Ex. 46                                                                             aniline                                                                              ethyl 6-(difluoro-                                                                         C.sub.19 H.sub.17 F.sub.5 N.sub.2 O.sub.3                                             182-183                                                                            C    54.80                                                                             54.69                                      methyl)-4-ethyl-5-        H    4.08                                                                              4.13                                       [(phenylamino)carbonyl]-  N    6.73                                                                              6.68                                       2-(trifluoromethyl)-3-                                                        pyridinecarboxylate                                            91 Ex. 47                                                                             ammonia gas                                                                          ethyl 5-(amino-                                                                            C.sub.14 H.sub.15 O.sub.3 N.sub.2 F.sub.5                                             141-143                                                                            C    47.46                                                                             47.64                                      carbonyl)-6-(difluoro-    H    4.27                                                                              4.32                                       methyl)-4- -n-propyl-2-   N    7.91                                                                              7.71                                       (trifluoromethly)-3-                                                          pyridinecarboxylate                                            __________________________________________________________________________

EXAMPLE 92 Preparation of ethyl5-cyano-6-(difluoromethyl)-4-ethyl-2-(trifluoromethyl)-3-pyridinecarboxylate

To 100 ml of phosphorus oxychloride in a 500 ml flask is added 3.5 g(0.0102 mole) of the product of Example 88. The mixture is refluxed for18 hours, concentrated, washed in water, and extracted with ethyl ether.The ether extracts are dried on anhydrous MgSO₄, concentrated, and driedunder vacuum to yield 1.23 g (37%) of the desired product, m.p. 38°-40°C.

Anal. Calc'd. for C₁₃ H₁₁ O₂ N₂ F₅ : C, 48.44; H, 3.41; N, 8.69. Found:C, 48.38; H, 3.48; N, 865.

EXAMPLE 93

Preparation of ethyl5-cyano-6-(difluoromethyl)-4-n-propyl-2-(trifluoromethyl)-3-pyridinecarboxylate

A mixture of 4.0 g (0.0112 mole) of the product of Example 91 and 100 gof phosphorus oxychloride is held at reflux for 20 hours andconcentrated. The residue is poured into water and extracted with ether.The ether extract is dried (MgSO₄) and concentrated. The residue waskugelrohr distilled at 0.1 torr to give 2.26 g of an oil which isrecrystallized from hexane at low temperature to give 1.11 g of thedesired product as a solid, m.p. 40°-41° C.

Anal. Calc'd. for C₁₄ H₁₃ F₅ N₂ O₂ : C, 50.01; H, 3.90; N, 8.33; Found:C, 49.75: H, 3.98; N, 8.21.

EXAMPLE 94 Preparation of diethyl2,6-bis(trifluoromethyl)-4-(1-3-butenyl)-3,5-pyridinedicarboxylate

A three-necked 250 ml flask is desiccated and purged with argon.Approximately 45 ml of dried tetrahydrofuran is injected into the flaskvia syringe. The flask is cooled at -78° C. and charged with 14 ml(0.0227 mole) of 1.6M n-butyl lithium followed by 2.96 ml (0.0227 mole)of diisopropyl amine. After stirring for 5 minutes, 8.8 g (0.0227 mole)of the product of Example 1 is diluted with 10 ml of driedtetrahydrofuran and injected into the flask. The mixture is stirred onehour. To this mixture is added 4.23 g (0.035 mole) of allyl bromide andthe mixture stirred for 90 minutes at room temperature.

The mixture is diluted with ethyl ether and washed successively withwater and 10% aqueous HCl. The organics are dried over MgSO₄ andconcentrated. Chromatography in 5% ethyl acetate/cyclohexane yields 1.4g (14.4%) of the desired product, n_(D) ²⁵ 1.4410.

Anal. Calc'd. for C₁₈ H₁₉ O₄ N₁ F₆ : C, 50.58; H, 4.44; N, 3.27; Found:C, 50.69; H, 4.47; N, 3.30.

EXAMPLE 95

Preparation of diethyl2,6-bis(trifluoromethyl)-4-(3-butenyl)-3,5-pyridinedicarboxylate

A three-necked 250 ml flask is heated, desiccated, and purged withargon. Tetrahydrofuran (50 ml) is injected via syringe and the flask iscooled to -78° C. To this is added 8.33 ml (0.0133 mole) of 1.6M n-butyllithium via syringe followed by 2 ml (0.0133 mole) of diisopropyl amine.To 10 ml of dried tetrahydrofuran, 5 g (0.0133 mole) of the product ofExample 2 is added and the solution is injected into the reactionmixture. The mixture is stirred for an hour. Allyl bromide, 2.4 g (0.02mole) is injected into the flask and the mixture is stirred for 90minutes at room temperature.

The mixture is diluted with ethyl ether and washed successively withwater and 10% HCl. The organics are dried, concentrated, andchromatographed with 5% ethyl acetate in cyclohexane to yield 0.7 g(29.26%) product; n_(D) ²⁵ 1.4365.

Anal. Calc'd. for C₁₇ H₁₇ O₄ N₁ F₆ : C, 49.39; H, 4.11; N, 3.39; Found:C, 49.54; H, 4.14; N, 3.36.

EXAMPLE 96 Preparation of ethyl 6-(difluoromethyl)4-ethyl-5-hydroxymethyl-2-(trifluoromethyl) 3-pyridinecarboxylate

To a dry 500 ml four-necked flask is charged 30.6 g (0.09 mole) of theproduct of Example 28 and 40 ml of tetrahydrofuran under nitrogen. Thereaction mixture is cooled to 10° C. with an ice-water bath. To theabove solution is added via a syringe 180 ml (0.18 mole) of 1M borane intetrahydrofuran. The reaction mixture is stirred for 160 hours andpoured into water. The organics are extracted into 300 ml of ether andthe ether extract washed with 200 ml of saturated sodium bicarbonate,dried (MgSO₄), and concentrated. The residue is crystallized frompetroleum ether to give 25 g (84.9%) of the desired product, m.p.59.5°-60.5° C.

Anal. Calc'd. for C₁₃ H₁₄ F₅ N₁ O₃ : C, 47.71; H, 4.31 ; N, 4.28; FoundC, 47.72; H, 4.31; N, 4.25.

EXAMPLE 97

Preparation of ethyl 6-(difluoromethyl)4-ethyl-5-formyl-2-(trifluoromethyl)-3-pyridinecarboxylate

A mixture of 4.74 g (0.0145 mole) of the product of Example 96, 8.6 g(0.0336 mole) of pyridinium chlorochromate, and 70 ml of CH₂ Cl₂ is heldat room temperature for 18 hours. The CH₂ Cl₂ solution is decanted andis chromatographed on silica gel using CH₂ Cl₂ as eluent. The first 2 Leluate gives 3.93 g (83.4%) of the desired product as white solid, m.p.63.5°-65° C.

Anal. Calc'd. for C₁₃ H₁₂ F₅ N₁ O₃ : C, 48.01; H, 3.72; N, 4.31; Found:C, 48.02; H, 3.74; N, 4.28.

EXAMPLE 98 Preparation of diethyl 2-(difluoromethyl)4-(2-methylsulfonylethyl)-6-trifluoromethyl-3, 5-pyridinedicarboxylate

To a solution of 12.0 g (0.0289 mole) of the product of Example 23 in200 ml of methylene chloride is added 13.0 g (0.064 mole)m-chloroperbenzoic acid. The reaction mixture is stirred for 24 hoursand poured into a mixture of 25 ml 10% sodium hydroxide and 400 ml ofwater. The methylene chloride layer is separated and washed successivelywith diluted sodium bicarbonate, sodium thiosulfate, saturated sodiumchloride, dried, and concentrated to give 12.9 g of a solid. A portion(5.0 g) of this solid is purified by HPLC using 33% ethylacetete/cyclohexane as eluent to give 3.6 g of the desired product, m.p.98°-101° C.

Anal. Calc'd. for C₁₆ H₁₈ F₅ N₁ O₆ S: C, 42.96; H, 4.06; N, 3.13; Found:C, 42.80; H, 4.06; N, 3.12.

EXAMPLE 99 Preparation of 3-ethyl 5-methyl6-(difluoromethyl)-4-vinyl-2-(trifluoromethyl)-3,5-pyridinedicarboxylate

A mixture of 17.31 g (0.0387 mole) of the product of Example 98, 2.16 g(0.054 mole) of sodium hydroxide, 125 ml of water, and 60 ml of ethanolis stirred for 24 hours and concentrated. The residue is stirred withether and 600 ml of 1.5 N sodium hydroxide. The aqueous layer isacidified with concentrated hydrochloric acid. The organic is extractedinto methylene chloride (2×400 ml). The methylene chloride extracts weredried and concentrated to give 11.67 g of a residue. A mixture of theabove residue, 14.70 g (0.104 ml) of methyl iodide, 14.3 (0.104 g mole)of potassium carbonate, and 300 ml of acetone is refluxed for 18 hoursand concentrated. The residue is stirred with 500 ml of water and 500 mlof ether. The ether layer is dried and concentrated. The residue (11.34g) is kugelrohr distilled at 0.3 torr to give 7.50 g (62%) of thedesired product, n_(D) ²⁵ 1.4567.

Anal. Calc'd. for C₁₄ H₁₂ F₅ N₁ O₄ :

C, 47.60; H, 3.42; N, 3.97;

Found: C, 47.46; H, 3.55; N, 3.85.

EXAMPLE 100 Preparation of diethyl4-[2-(methylsulfinyl)-ethyl]-2-(difluoromethyl)-6-(trifluoromethyl)-pyridine-3,5-dicarboxylate

To a stirred solution of 20.09 g (0.048 mole) of product of Example 23in 50 ml methylene chloride cooled in an ice bath is added a solution of10.3 g (0.050 moles) of m-chloroperbenzoic acid in 100 ml methylenechloride holding the reaction temperature below 10° C. Stirring andcooling with an ice bath is continued for one hour after addition iscomplete.

The resulting slurry is poured into a solution prepared from 25 ml 10%sodium hydroxide and 600 ml of water. After mixing well, the phases areseparated. The aqueous phase is extracted with 50 ml methylene chloride.The methylene chloride phases are combined, washed successively withsolution, 600 ml of 0.5% sodium bicarbonate, 0.5% sodium chloridesolution, dried over magnesium sulfate, filtered, and stripped, to give20.5 g of light yellow solid.

The product is purified by recrystallizing twice from hexane/ether togive 12.5 g of white solid, m.p. 90.5°-91.5° C., 60% yield.

Anal. Calc'd. for C₁₆ H₁₈ F₅ N₁ O₅ S₁ :

C, 4%.55; H, 4.21; N, 3.25;

Found: C, 44.45; H, 4.22; N, 3.20.

EXAMPLE 101

Preparation of 3-ethyl 5-methyl6-(difluoromethyl)-4-(methylthiomethyl)-2-(trifluoromethyl)-3,5-pyridinedicarboxylate

A mixture of 32.8 g (0.081 mole) of the crude product of Example 25, 37g of 10% sodium hydroxide, 35 ml of water, and 125 ml of ethanol isstirred for one hour and concentrated. The residue is stirred with 700ml of water and 200 ml of methylene chloride. The aqueous layer is madeacidic and the precipitate is extracted into methylene chloride. Themethylene chloride extract is dried and concentrated to give 19.9 g ofan acid, m.p. 81°-85° C. A portion (10.6 g, 0.1078 mole) of this acid,5.2 ml (0.085 mole) of methyl iodide, 11.8 g (0.085 mole) of potassiumcarbonate, and 150 ml of acetone are mixed and held at reflux for 24hours. The reaction mixture is concentrated and the residue is stirredwith 150 ml of methylene chloride and 200 ml of water. The methylenechloride layer is dried and concentrated. The residue is kugelrohrdistilled at 0.25 torr (pot temperature 135°-170° C.) to give 7.16 g ofa distillate. This distillate is purified by HPLC using 7% ethylacetate/cyclohexane as eluent.

The earlier fraction (retention time 4-6 min) gives 4.75 g of a solidwhich is recrystallized twice from hexane/ether to give 2.78 g of thedesired product, m.p. 67°-68.5° C.

Anal. Calc'd. for C₁₄ H₁₄ F₅ N₁ O₄ S₁ :

C, 43.41; H, 3.64; N, 3.62;

Found C, 43.13; H, 3.61; N, 3.55.

EXAMPLE 102 Preparation of diethyl6-(difluoromethyl)-2-(trifluoromethyl)-4-vinyl-3,5-pyridinedicarboxylate

A mixture of 3.7 g of product of Example 99, 13.75 g of 10% sodiumhydroxide, and 10 ml of water is stirred for 24 hours and concentrated.The residue is stirred with 300 ml of water and 50 ml of methylenechloride. The aqueous layer is acidified with concentrated hydrochloricacid and extracted with methylene chloride. The methylene chlorideextract is dried and concentrated to give 2.99 g of a yellow solid whichis recrystallized from petroleum ether to give 2.01 g of a white solid.A mixture of this solid, 1 ml of ethyl iodide, 10 ml of DMF, and 2.09 gof potassium carbonate is stirred for 24 hours and poured into 300 ml ofwater. The reaction mixture is extracted with methylene chloride and themethylene chloride extract dried and concentrated. The residue iskugelrohr distilled at 0.1 torr to give 1.41 g of the desired product,n_(D) ²⁵ 1.4529.

Anal. Calc'd. for C₁₅ H₁₄ F₅ N₁₁ O₄ :

C, 49.05; H, 3.84; N, 3.81

Found: C, 49.09; H, 3.84; N, 3.81.

EXAMPLE 103

Preparation of diethyl 4-[(1-ethoxy)methoxymethyl]-2-(difluoromethyl)-6-(trifluoromethyl)-pyridine-3,5-dicarboxylate

To a stirred solution of 4.0 g (0.010 mole) of the product of Example24% in 30 ml of carbon tetrachloride is added 2.5 g (0.015 mole) ofbromine. The solution is cooled to 10° C., a stream of dry nitrogen ispassed over the reaction mixture (to purge hydrogen bromide), and thereaction is illuminated with a 150 watt spotlight. The reactiontemperature is held at 10°-15° C. for 6 hours. The light is removed andthe nitrogen stream stopped.

A solution of 1.41 g (0.013 mole) 2, 6-lutidine in 5 ml absolute ethanolis added to the reaction mixture, and this resulting reaction mixture isstirred for 18 hours at ambient temperature.

The reaction mixture is poured into 100 ml water with 50 ml methylenechloride. After mixing well, the organic phase is separated, washed with100 ml of 0.50% hydrochloric acid solution, 100 ml of 1% sodiumbicarbonate, dried over magnesium sulfate, filtered, and stripped togive 4.29 g of yellow oil.

The product is purified by HPLC on silica gel using 10% ethylacetate incyclohexane as a solvent to give 2.18 g of light yellow oil, yield 48%,n_(D) ²⁵ 1.4446.

Anal. Calc'd. for C₁₇ H₂₀ F₅ N₁ O₆ :

C, 47.56; H, 4.70; N, 3.26;

Found: C, 47.55; H, 4.71; N, 3.26.

In a manner similar to the procedure of Example 103, the product ofExample 24 is brominated and the resulting product is reacted with anappropriate alcohol or alkylthiol as indicated in the following examplesas noted in Table 15 to provide the product listed.

                                      TABLE 15                                    __________________________________________________________________________    Ex.                                                                              Starting               Empirical   Analysis %                              No.                                                                              Material                                                                           Reactant                                                                             Product    Formula n.sub.D .sup.25                                                                   Element                                                                            Calc'd                                                                            Found                          __________________________________________________________________________    104                                                                              Ex. 71                                                                             methanol                                                                             3-ethyl 5-methyl 6-                                                                      C.sub.15 H.sub.16 F.sub.5 N.sub.1 O.sub.6                                             1.4428                                                                            C    44.90                                                                             44.71                                         (difluoromethyl)-4-    H    4.02                                                                              3.81                                          (dimethoxymethyl)-2-   N    3.49                                                                              3.45                                          (trifluoromethyl)-3,5-                                                        pyridinedicarboxylate                                          105                                                                              Ex. 71                                                                             methanethiol                                                                         3-ethyl 5-methyl 6-                                                                      C.sub.15 H.sub.16 F.sub.5 NO.sub.5 S                                                  1.4457                                                                            C    43.17                                                                             43.06                                         (difluoromethyl)-4-    H    3.86                                                                              3.68                                          [methoxy(methylthio)-  N    3.36                                                                              3.34                                          methyl]-2-(trifluoro-                                                         methyl-3,5-pyridinedi-                                                        carboxylate                                                    __________________________________________________________________________

In a manner similar to Example 39, additional pyridinedicarboxylic acidsof this invention are prepared as indicated in Table 16.

                                      TABLE 16                                    __________________________________________________________________________    Ex.           Starting                                                                           Empirical                                                                            m.p.   Analysis %                                   No.                                                                              Compound   Material                                                                           Formula                                                                              °C.                                                                           Element                                                                            Calc'd                                                                            Found                               __________________________________________________________________________    106                                                                              2-(difluoromethyl)-                                                                      Ex. 26                                                                             C.sub.13 H.sub.12 F.sub.5 NO.sub.4                                                   222-225.5                                                                            C    45.76                                                                             45.71                                  4-(1-methylpropyl)-           H    3.54                                                                              3.71                                   6-(trifluoromethyl)-          N    4.10                                                                              3.88                                   3,5-pyridinedi-                                                               carboxylic acid                                                            107                                                                              2-(difluoromethyl)-                                                                      Ex. 27                                                                             C.sub.14 H.sub.14 F.sub.5 NO.sub.4                                                   247-249                                                                              C    47.16                                                                             47.33                                  4-(2,2-dimethyl-              H    4.03                                                                              3.97                                   propyl)-6-trifluoro-          N    3.94                                                                              3.94                                   methyl)-3,5-pyridine-                                                         dicarboxylic acid                                                          108                                                                              2-(difluoromethyl)-                                                                      Ex. 17                                                                             C.sub.12 H.sub.8 F.sub.5 N.sub.1 O.sub.4                                             260-264 (dec)                                                                        C    44.32                                                                             44.22                                  4-cycloproply-6-              H    2.48                                                                              2.52                                   (trifluromethyl)-             N    4.31                                                                              4.26                                   3,5-pyridinedi-                                                               carboxylic acid                                                            __________________________________________________________________________

In a manner similar to the procedure of Example 69, otherpyridinedicarboxylates of this invention are prepared, with theexception that the reactions are conducted at room temperature. As notedabove with respect to Table 10, having due regard for starting materialsubstituted and reaction conditions suitable for the reactants employed,additional examples are provided as shown in Table 17.

                                      TABLE 17                                    __________________________________________________________________________    Ex.                                                                              Starting       Solvent-       Emperical   m.p. Analysis %                  No.                                                                              Material                                                                           Reactant  Condition                                                                           Product  Formula n.sub.D .sup.25                                                                   °C.                                                                         Element                                                                            Calc'd                                                                            Found              __________________________________________________________________________    109                                                                              Ex. 43                                                                             K.sub.2 CO.sub.3 --                                                                     DMF   dipropyl 2-                                                                            C.sub.19 H.sub.24 F.sub.5 NO.sub.4                                                    1.4473   C    53.65                                                                             53.68                      CH.sub.3 CH.sub.2 CH.sub.2 I                                                                  (difluoro-                H    5.69                                                                              5.65                                       methyl-4-                 N    3.29                                                                              3.26                                       isobutyl-6-                                                                   (trifluoro-                                                                   methyl)3,5-                                                                   pyridine-                                                                     dicarboxylate                                         110                                                                              Ex. 107                                                                            K.sub.2 CO.sub.3 --                                                                     DMF   dimethyl 2-                                                                            C.sub.16 H.sub.18 F.sub.5 NO.sub.4                                                        77.5-77.8                                                                          C    50.13                                                                             50.06                      CH.sub.3 I      (difluoro-                H    4.73                                                                              4.49                                       methyl)-4-                N    3.65                                                                              3.61                                       (2,2-dimethyl-                                                                propyl)-6-                                                                    (trifluoro-                                                                   methyl)-3,5-                                                                  pyridinedi-                                                                   carboxylate                                           111                                                                              Ex. 106                                                                            K.sub.2 CO.sub.3 --                                                                     DMF   dimethyl 2-                                                                            C.sub.15 H.sub.16 F.sub.5 NO.sub.4                                                    1.4515   C    48.79                                                                             48.90                      CH.sub.3 I      (difluror-                H    4.37                                                                              4.39                                       methyl)-4-                N    3.79                                                                              3.77                                       (1-methyl-                                                                    propyl)-6-                                                                    (trifluoro-                                                                   methyl)-3,5-                                                                  pyridinedi-                                                                   carboxylate                                           112                                                                              Ex. 41                                                                             K.sub.2 CO.sub.3 --                                                                     DMF   dipropargyl                                                                            C.sub.18 H.sub.14 F.sub.5 NO.sub.4                                                    1.4698   C    53.61                                                                             53.60                      H--C≡C--CH.sub.2 Br                                                                     2-(difluoro-              H    3.50                                                                              3.52                                       methyl)-4-                N    3.47                                                                              3.43                                       isopropyl-6-                                                                  (trifluoro-                                                                   methyl)-3,5-                                                                  pyridine-                                                                     dicarboxylate                                         113                                                                              Ex. 39                                                                             K.sub.2 CO.sub.3 --                                                                     DMF   dipropargyl                                                                            C.sub.18 H.sub.14 F.sub.5 NO.sub.4                                                    1.4713   C    53.61                                                                             53.74                      H--C≡C--CH.sub.2 Br                                                                     2-(difluoro-              H    3.50                                                                              3.54                                       methyl)-4-                N    3.47                                                                              3.44                                        -n-propyl-6-                                                                 (trifluoro-                                                                   methyl)-3,5-                                                                  pyridinedi-                                                                   carboxylate                                           114                                                                              Ex. 108                                                                            K.sub.2 CO.sub.3 --                                                                     DMF   dimethyl C.sub.14 H.sub.12 F.sub.5 N.sub.1                                             O.sub.4     77-79                                                                              C    47.60                                                                             47.64                      CH.sub.3 I      4-cyclopropyl-            H    3.42                                                                              3.44                                       2-(difluoro-              N    3.97                                                                              3.92                                       methyl)-6-                                                                    (trifluoro-                                                                   methyl-3,5-                                                                   pyridinedi-                                                                   carboxylate                                           115                                                                              Ex. 108                                                                            K.sub.2 CO.sub.3 --                                                                     DMF   dipropargyl                                                                            C.sub.18 H.sub.12 F.sub.5 N.sub.1                                             O.sub.4 1.4783   C    53.87                                                                             53.46                      HC≡CCH.sub.2 Br                                                                         4-cyclopropyl-            H    3.01                                                                              3.27                                       2-(difluror-              N    3.49                                                                              3.45                                       methyl)-6-                                                                    (trifluoro-                                                                   methyl)-3,5-                                                                  pyridinedi-                                                                   carboxylate                                           116                                                                              Ex. 37                                                                             K.sub.2 CO.sub.3 --                                                                     DMF   3-ethyl  C.sub.18 H.sub.20 F.sub.5 N.sub.1                                             O.sub.4 1.4654   C    52.81                                                                             52.73                      CH.sub.3 I      5-methyl 4-               H    4.92                                                                              4.93                                       cyclohexyl-2-             N    3.42                                                                              3.39                                       (trifluoro-                                                                   methyl)-6-                                                                    (difluoro-                                                                    methyl)-3,5-                                                                  pyridinedi-                                                                   carboxylate                                           __________________________________________________________________________

EXAMPLE 117 Preparation of 3-methyl 5-propargyl2-(difluoromethyl)-4-n-propyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylat

A mixture of 5.06 g (0.0125 mole) of product of Example 113, 1.24 g(0.0188 mole) of 85% potassium hydroxide, 65 ml of ethanol, and 50 ml ofwater is stirred for 48 hours and then extracted with ether. The aqueouslayer is acidified with 30 ml of concentrated hydrochloric acid. Theoily precipitate is extracted into 100 ml of ether. The ether extract isdried (MgSO₄) and concentrated to give 3.99 g of a solid, m.p. 91°-94°C.

A portion (2.14 g, 0.0058 mole) of the above solid, 0.80 g (0.0058 mole)of potassium carbonate, 0.99 g (0.007 mole) of methyl iodide, and 60 mlof DMF is stirred for 72 hours and poured into 200 ml of water. The oilyprecipitate is extracted twice with 100 ml of ether. The combined etherextracts were dried over magnesium sulfate and concentrated. The residueis kugelrohr distilled to give 1.21 g (55.3%) of the desired product asan oil, n_(D) ²⁵ 1.4556.

Anal. Calc'd. for C₁₆ H₁₄ F₅ NO₄ :

C, 50.67; H, 3.72; N, 3.67;

Found: C, 50.57; H, 3.73; N, 3.67.

In a manner similar to Examples 28, 29, and 30, other2-(difluoromethyl)-6-(trifluoromethyl)-3,5-pyridinedicarboxylic acid5-monoester of this invention are prepared.

Having due regard for starting materials substituted and the reactioncondition suitable for the reactant employed, additional examples areprovided as noted in Table 18.

                                      TABLE 18                                    __________________________________________________________________________    Ex.                                                                              Starting                                                                           Solvent-           Empirical                                                                            m.p.  Analysis %                            No.                                                                              Material                                                                           Condition                                                                            Product     Formula                                                                              °C.                                                                          Element                                                                            Calc'd                                                                            Found                        __________________________________________________________________________    118                                                                              Ex. 112                                                                            ethanol-                                                                             2-(difluoromethyl)-4-                                                                     C.sub.15 H.sub.12 F.sub.5 NO.sub.4                                                   89-92 C    49.32                                                                             49.03                                water; room                                                                          isopropyl-6-(trifluoro-  H    3.31                                                                              3.35                                 temperature                                                                          methyl)-3,5-pyridine-    N    3.83                                                                              3.79                                        dicarboxylic acid                                                             5-propargyl ester                                              119                                                                              Ex. 27                                                                             ethanol-                                                                             2-(difluoromethyl)-4-                                                                     C.sub.16 H.sub.18 F.sub.5 NO.sub.4                                                     110-111.5                                                                         C    50.13                                                                             50.04                                water; room                                                                          (2,2-dimethylpropyl)-    H    4.73                                                                              4.78                                 temperature                                                                          6-(trifluoromethyl)-     N    3.65                                                                              3.60                                        3,5-pyridinedicarboxylic                                                      acid 5-ethyl ester                                             120                                                                              Ex. 26                                                                             ethanol-                                                                             2-(difluoromethyl)-4-                                                                     C.sub.15 H.sub.16 F.sub.5 NO.sub.4                                                   83.5-85.5                                                                           C    48.79                                                                             48.86                                water; room                                                                          (1-methylpropyl)-6-      H    4.37                                                                              4.38                                 temperature                                                                          (trifluoromethyl)-3,5-   N    3.79                                                                              3.77                                        pyridinedicarboxylic                                                          acid 5-ethyl ester                                             121                                                                              Ex. 72                                                                             ethanol-                                                                             2-(difluoromethyl)-4-                                                                     C.sub.13 H.sub.12 F.sub.5 NO.sub.4                                                   114-116                                                                             C    45.76                                                                             45.86                                water; room                                                                          isopropyl-6-(tri-        H    3.54                                                                              3.57                                 temperature                                                                          fluoromethyl)-3,5-       N    4.10                                                                              4.10                                        pyridinedicarboxylic                                                          acid 5-methyl ester                                            __________________________________________________________________________

In a manner similar to the procedure of Example 69, otherpyridinedicarboxylates of this invention are prepared from theappropriate monoacids. Having due regard for starting materialsubstituted and reaction condition suitable for the reactants employed,additional examples are provided a noted in Table 19.

                                      TABLE 19                                    __________________________________________________________________________    Ex.                                                                              Starting      Solvent-           Empirical   Analysis %                    No.                                                                              Material                                                                            Reactant                                                                              Condition                                                                            Product     Formula n.sub.D.sup.25                                                                    Element                                                                             Calc'd                                                                            Found               __________________________________________________________________________    122                                                                              Ex. 77                                                                              K.sub.2 CO.sub.3 --                                                                   DMF; room                                                                            5-methyl 3-propargyl                                                                      C.sub.16 H.sub.14 F.sub.5 NO.sub.4                                                    1.4582                                                                            C     50.67                                                                             50.54                        HC.tbd.CCH.sub.2 Br                                                                   temperature                                                                          2-(difluoromethyl)-     H     3.72                                                                              3.79                                        4-n-propyl-6-           N     3.69                                                                              3.61                                        (trifluoromethyl)-                                                            3,5-pyridinedi-                                                               carboxylate                                           123                                                                              Ex. 120                                                                             K.sub.2 CO.sub.3 --                                                                   DMF; room                                                                            3-ethyl 5-methyl                                                                          C.sub.16 H.sub.18 F.sub.5 N.sub.1                                             O.sub.4 1.4500                                                                            C     50.19                                                                             49.90                        CH.sub.3 I                                                                            temperature                                                                          6-(difluoromethyl)-     H     4.73                                                                              4.78                                        4-(1-methylpropyl)-     N     3.65                                                                              3.59                                        2-(trifluoromethyl)-                                                          3,5-pyridinedi-                                                               carboxylate                                           124                                                                              Ex. 119                                                                             K.sub.2 CO.sub.3 --                                                                   DMF; room                                                                            3-ethyl 5-methyl                                                                          C.sub.17 H.sub.20 F.sub.5 NO.sub.4                                                    1.4538                                                                            C     51.39                                                                             51.34                        CH.sub.3 I                                                                            temperature                                                                          6-(difluoromethyl)-     H     5.07                                                                              5.07                                        4-(2,2-dimethyl-        N     3.53                                                                              3.53                                        propyl)-2-(tri-                                                               fluoromethyl)-3,5-                                                            pyridinedicarboxylate                                 125                                                                              Ex. 118                                                                             K.sub.2 CO.sub.3 --                                                                   DMF; room                                                                            3-methyl 5-propargyl                                                                      C.sub.16 H.sub.14 F.sub.5 NO.sub.4                                                    1.4589                                                                            C     50.67                                                                             50.47                        CH.sub.3 I                                                                            temperature                                                                          2-(difluoromethyl)-     H     3.72                                                                              3.78                                        4-isopropyl-6-(tri-     N     3.69                                                                              3.65                                        fluoromethyl)-3,5-                                                            pyridinecarboxylate                                   __________________________________________________________________________

EXAMPLE 126

Preparation of diethyl2-(difluoromethyl)-4-(4-pyridyl)-6-(trifluoromethyl)-3,5-pyridinedicarboxylate

In a manner similar to the procedure of Example 13, product of Exampless of Table 3 is reacted with 1,8-diaza-bicyclo-[5.4.0]-undec-5-ene togive the desired product as a solid, m.p. 43°-45° C.

Anal. Calc'd. for C₁₈ H₁₅ F₅ N₂ O₄ :

C, 51.68; H, 3.61; N, 6.70;

Found: C, 51.51; H, 3.63; N, 6.66.

EXAMPLE 127 Preparation of 3-ethyl 5-methyl6-(difluoromethyl)-4-(2-oxiranyl)-2-(trifluoromethyl)-3,5-pyridinedicarboxylate

A stirred mixture of 14.0 g (0.039 mole) of product of Example 99, 105ml of ethanol, 70 ml (0.60 mole) of 30% hydrogen peroxide, and 2.9 g(0.033 mole) of sodium bicarbonate is heated at 70° C. for 3 hours. Thereaction mixture is cooled and concentrated in vacuo to approximately 30ml then extracted with 75 ml of methylene chloride. The methylenechloride solution is washed with 300 ml of water. The aqueous layer isextracted twice with 75 ml of methylene chloride. The combined methylenechloride extracts were dried over magnesium sulfate and concentrated.The residue is purified by HPLC using 8% ethyl acetate/cyclohexane aseluent to give a yellow solid which after recrystallization fromhexane/ether gave 2.32 g of the desired product as a white solid; m.p.57.5°-59° C.

Anal. Calc'd. for C₁₄ H₁₂ F₅ NO₅ :

C, 45.54; H. 3.28; N, 3.79;

Found: C, 45.63; H, 3.28; N, 3.77.

EXAMPLE 128

Preparation of 3-ethyl 5-methyl 4-(1,2-dibromoethyl)-6-(difluoromethyl)-2-(trifluoromethyl)-3,5-pyridinedicarboxylate

A solution of 3.0 g (0.084 mole) of product of Example 99, 1.49 g (0.091mole) of bromine in 30 ml of carbon tetrachloride is stirred for 3 daysand concentrated. The residue is kugelrohr distilled at 0.1 torr (pottemperature, 140°-150° C.) to give 3.45 g (80%) of the desired productas an oil, n_(D) ²⁵ 1.4950.

Anal. Calc'd. for C₁₄ H₁₂ Br₂ F₅ NO₄ :

C, 32.77; H, 2.36; N, 2.73;

Found C, 33.00; H, 2.39; N, 2.93.

EXAMPLE 129 Preparation of 3-ethyl 5-methyl4-(1-bromoethenyl)-6-(difluoromethyl)-2-(trifluoromethyl)-3,5-pyridinedicarboxylate

To a stirred mixture of 0.49 g (0.012 mole) of 60% sodium hydride in oildispersion and 4 ml of anhydrous THF is added 10 ml of methanol undernitrogen. The reaction mixture is cooled with an ice bath to 5° C. thentreated slowly with a solution of 3.0 g (0.0058 mole) of product ofExample 128 in 2 ml of anhydrous THF, while the reaction mixture ismaintained below 15° C. The mixture is stirred at 0° C. for 2 hours andpoured into 180 ml of 1% hydrochloric acid then extracted three timeswith 50 ml of methylene chloride. The combined methylene chlorideextracts are dried over magnesium sulfate and concentrated. The residueis purified by a radially-accelerated preparatory TLC using 10% ethylacetate/cyclohexane as eluent to give 0.85 g (33%) of the desiredproduct as a light yellow oil, n_(D) ²⁵ 1.4734.

Anal. Calc'd. for C₁₄ H₁₁ BrF₅ NO₄ :

C, 38.91; H, 2.57; N, 3.29;

Found: C, 39.00; H, 2.64; N, 3.37.

EXAMPLE 130 Preparation of 3-ethyl 5-methyl 6-(difluoromethly)-b4-methylsulfonylmethyl-2-(trifluoromethyl)-3,5-pyridinedicarboxylate

To a cold (15° C.) stirred solution of 0.5 g (0.0012 mole) of product ofExample 101 in 20 ml of methylene chloride is added 0.55 g ofm-chloroperbenzoic acid in portion. The reaction mixture is stirred atambient temperature for 16 hours, poured into 150 ml of 1% aqueoussodium hydroxide. The methylene chloride layer is separated, washed with100 ml of water, dried over magnesium sulfate, and concentrated in vacuoto give a white solid. Recrystallization from ether/hexane gives 0.46 gof the desired product as a white solid, m.p. 110.5°-11.5° C.

Anal. Calc'd. for C₁₄ H₁₄ F₅ NO₆ S:

C, 40.10; H, 3.37; N, 3.34;

Found: C, 39.97; H, 3.37; N, 3.33.

EXAMPLE 131 Preparation of dimethyl2-(difluoromethyl)-4-methylthiomethyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylate

A mixture of 25.0 g (0.062 mole) of product of Example 25, 100 ml of 10%aqueous sodium hydroxide, 40 ml of ethanol, and 150 ml of water is heldat reflux for 48 hours and concentrated to approximate 150 ml. Theresidual solution is diluted with 1 L of water and acidified to pH 1-2with concentrated hydrochloride acid. The aqueous mixture is extractedthree times with 300 ml of ether. The combined ether extracts are driedover magnesium sulfate and concentrated to give 11.7 g (55%) of a solid,m.p. 209°-210° C.

A mixture of 7.08 g (0.0226 mole) of above solids, 3.0 ml (0.0475 mole)of methyl iodide, 3.45 g (0.025 mole) of potassium carbonate, and 35 mlof DMF is stirred for 16 hours. The reaction mixture is poured into 300ml of 1% hydrochloride acid and extracted with 100 ml of methylenechloride. The methylene chloride solution is washed successively with200 ml of water and 200 ml of 1% sodium bicarbonate, dried overmagnesium sulfate, and concentrated. The residue is kugelrohr distilledat 0.15 torr (pot temperature, 120°-125° C.) to give a white solid whichis recrystallized from ether/hexane to give 3.0 g (36%) of the desiredproduct, m.p. 50.5°-51.5° C.

Anal. Calc'd. for C₁₃ H₁₂ F₅ NO₄ S:

C, 41.83; H, 3.24 ; N, 3.75;

Found: C, 41.84; H, 3.25; N, 3.75.

EXAMPLE 132 Preparation of dimethyl 2-(difluoromethyl)4-iodomethyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylate

A mixture of 10.43 g (0.033 mole) of the solid (m.p. 209°-210° C.)described in Example 131, 8.2 ml (0.132 mole) of methyl iodide, 20.2 g(0.146 mole) of potassium carbonate, and 45 ml of DMF is stirred atambient temperature for 5 days. The reaction mixture is poured into 550ml of 1% aqueous hydrochloric acid and extracted three times with 100 mlof methylene chloride. The combined extracts are washed successivelywith 1% hydrochloride acid, 1% sodium bicarbonate, and 10% sodiumchloride, dried over magnesium sulfate, and concentrated. The residualis purified by HPLC using 15% ethyl acetate/cyclohexane as eluent togive a yellow oil which crystallizes after standing. Recrystallizationtwice from ether/hexane gives 2.27 g (15%) of the desired product as awhite solid, m.p. 78°-79° C.

Anal. Calc'd. for C₁₂ H₉ F₅ INO₄ :

C, 31.81; H, 2.00; N, 3.09;

Found: C, 31.95; H, 1.90; N, 3.07.

EXAMPLE 133 Preparation of 3-ethyl 5-methyl2-(difluoromethyl)-4-methylthiomethyl-6-(trifluoromethyl)-3,5-pyridinecarboxylate

A mixture of 2.8 g (0.0077 mole) of product of Example 131, 3.7 g(0.0092 mole) of 10% sodium hydroxide, 3 ml of water, and 20 ml ofethanol is stirred at ambient temperature for 51/2 hours, andconcentrated. The residue is dissolved in 150 ml of water and extractedtwice with 50 ml of methylene chloride. The aqueous layer is acidifiedto pH 1-2 with concentrated hydrochloride acid and extracted three timeswith methylene chloride. The combined methylene chloride extracts aredried over magnesium sulfate and concentrated to give 2.6 g of a solid.

A mixture of 2.47 g (0.0066 mole) of the above solid, 1.28 g (0.0082mole) of ethyl iodide, 0.71 g (0.051 mole) of potassium carbonate, and20 ml of DMF is stirred for 48 hours and poured into 200 ml of 1%hydrochloride acid. The mixture is extracted three times with 50 ml ofmethylene chloride. The combined methylene chloride extracts are washedsuccessively with 150 ml of 1% sodium chloride and 150 ml of 1% sodiumbicarbonate, dried over magnesium sulfate, and concentrated. The residueis kugelrohr distilled at 0.3 torr. The distillate (collected at pottemperature of 120°-130° C.) is further purified by radially-acceleratedpreparatory TLC using 10% ethylene acetate/cyclohexane to give an oil.Kugelrohr distillation of this oil at 0.15 torr (collected at pottemperature of 125°-130° C.) gives the desired product as a light yellowoil, n_(D) ²⁵ 1.4750.

Anal. Calc'd. for C₁₄ H₁₄ F₅ NO₄ S: C, 43.41; H, 3.64; N, 3.62; Found:C, 43.42; H, 3.65; N, 3.62.

EXAMPLE 134 Preparation of 3-ethyl 5-methyl6-(di-fluoromethyl)-4-methyl-2(trifluoromethyl)-3,5-pyridinedicarboxylate

This product is isolated as a by-product in the preparation of theproduct of Example 101. The crude material is purified ty HPLC as notedin Example 101. After removal of the product of Example 101, the laterfraction gives 1.42 g of a yellow oil which is kugelrohr distilled at0.5 torr (pot temperature of 125°-135° C.) to give 1.35 g of the desiredproduct, n_(D) ²⁵ 1.4483.

Anal. Calc'd. for C₁₃ H₁₂ F₅ NO₄ : C, 45.76; H, 3.54; N, 4.1O; Found: C,45.76; H, 3.52; N,4.08.

EXAMPLE 135 Preparation of [3-carbomethoxy-5-carbethoxy-2-(difluoromethyl)-6-(trifluoromethyl)]-4-pyridylmethyl-dimethylsulfoniumtetrafluoroborate

To a solution of 19.9 g (0.0513 mole) of product of Example 101 in 150ml of acetonitrile under nitrogen is added 10.0 g (0.051 mole) of silvertetrafluoroborate followed immediately by 4.6 ml (0.075 mole) of methyliodide. The reaction mixture is stirred at ambient temperature for 16hours, then maintained at 45° for 24 hours. The grayish precipitate isfiltered. The filtrate is concentrated to a light brown oil whichcrystallizes upon standing. Recrystallization from ether-tetrahydrofurangives 21.6 g (86% yield) of the desired product as a white solid, mp119.5°-121°.

Anal. Calc'd. for C₁₅ H₁₇ BF₉ NO₄ S: C, 36.83; H, 3.50; N, 2.86; Found:C, 36.86; H, 3.46; N, 2.76.

EXAMPLE 136 Preparation of 5-ethyl-3-methyl2-(di-fluoromethyl)-4-(N,N-dimethylaminomethyl)-6-(tri-fluoromethyl)-3,5-pyridinedicarboxylate

To a stirred solution of 3.0 g (0.0061 mole) of product of example 135in 15 ml of N, N-dimethylformamide under nitrogen is added 1.4 g (0.0093mole) of sodium iodide. The reaction mixture is stirred at 25° for 1/2hour, then treated with 2.3 g (0.0091 mole) of an 18% solution ofdimethylamine in ether. After stirring at ambient temperature for 1/2hour, the reaction mixture is poured into a mixture of 500 ml of waterand 100 ml of saturated sodium chloride solution. The organic isextracted into ether (4×75 ml). The ether extracts are combined andwashed with 200 ml of 10% sodium chloride solution, dried over magnesiumsulfate and concentrated. The residue is purified by HPLC using 5% ethylacetate in cyclohexane as eluent. The desired fraction is concentrated.The residue is kugelrohr distilled at 0.1 torr (pot temperature120°-130°) to give 1.98 g (84% yield) of a water white oil, n²⁵ D1.4518.

Anal. Calc'd. for C₁₅ H₁₇ F₅ N₂ O₄ : C, 46.88; H, 4.46; N, 7.29 Found:C, 46.70; H, 4.45; N, 7.23.

EXAMPLE 137 Preparation of 5-ethyl-3-methyl2-(di-fluoromethyl-4-(N-ethyl-N-methylaminomethyl)-6-(tri-fluoromethyl)-3,5-pyridinedicarboxylate

To a stirred solution of 4.0 g (0.0081 mole) of product of Example 135in 25 ml of N, N-dimethylformamide cooled to 5° with an ice bath isadded 1.84 g (0.012 mole) of sodium iodide. The reaction mixture isstirred at 0°-5° for 1 hour, then allowed to warm to ambienttemperature. N-ethyl-N-methylamine (1.05 g, 0.017 mole) is added to thereaction mixture and the reaction mixture is stirred for 2 hours atambient temperature, then poured into a mixture of 300 ml of water and100 ml of saturated sodium chloride solution. The organic is extractedinto ether (4×100 ml) and the combined ether extracts are washed with200 ml of 10% sodium chloride solution, dried over magnesium sulfate andconcentrated. The residual oil is purified by radially-acceleratedpreparatory TLC followed by kugelrohr distillation at 0.15 torr (pottemperature 120°-130°) to give 2.49 g (77% yield) of the desired productas a yellow Oil, n²⁵ D 1.4534. Anal. Calc'd. for C₁₆ H₁₉ F₅ N₂ O₄ : C,48.24; H, 4.81; N, 7.03 Found: C, 48.10; H, 4.83; N, 6.99.

Compounds of this invention may be prepared from corresponding compoundsin which the R₁ or R₂ group contains one more fluorine atom than doesthe product compound. This scheme, which has been discussed earlier,involves one or more additional sequences of sodium borohydridereduction to the corresponding 1,2-dihydropyridine followed bydehydrofluorination in the presence of a nonaqueous organic base such asDBU or 2, 6-lutidine. This reaction pattern may be shown schematicallyas follows: ##STR46## However, this process is not restricted to thesituation in which one of R₁ and R₂ is CF₃. The reaction appliesequally, for example, when R₂ is CF₂ H, CFH₂, or alkyl and R₁ is to bedehydrofluorinated. The following Examples 138 and 139 show thepreparation of compounds of this invention in which one of R₁ and R₂ isCF₃ and the other is selected from CFH₂ and CH₃.

EXAMPLE 138 Preparation of dimethyl2-(fluoromethyl)-4-isobutyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylate

To a solution of 50.3 g (0.136 mole) of product of example 14 in 200 mlof DMF is added 21.3 g (0.563 mole) of sodium borohydride. The reactionmixture becomes exothermic and the temperature of the reaction mixturerises to 65° C. and subsides to 40° C. after 40 min. of stirring. To thereaction mixture is added 15 ml of water. The exothermic reactionmixture is cooled by an ice-water bath to 40° C. The cooling bath isremoved and the reaction mixture is stirred for 20 min. before beingpoured into 1 L of water. The organic is extracted into 500 ml ofmethylene chloride. The methylene chloride extract is dried overmagnesium sulfate and concentrated. The residual oil (44.5 g) ispurified by HPLC using 5% ethyl acetate in cyclohexane as eluent. Thefirst 2.8 L of eluate gives 7.6 g of an oil which contains 56% of thedesired product, 22% of the starting material, and 22% of anunidentified material. The second 2.5 L of eluate gives 24.6 g of an oilwhich contains a mixture of dimethyl2-(difluoromethyl)-1,2-dihydro-4-isobutyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylate(E) and dimethyl6-(difluoromethyl)-1,2-dihydro-4-isobutyl-2-(trifluoromethyl)-3,5-pyridinedicarboxylate(F) and other unidentified products. This oil is crystallized fromether-hexane to give 7.4 g (15%) of a solid, mp 82°-85° C., which is a4.6:1 mixture of above mentioned (E) and (F). The mother liquor isconcentrated to an oil (15.6 g) which contains (E), (F), and otherunidentified products. A solution of above oil, 9.0 g (0.0568 mole) ofDBU and 100 ml of ether is stirred for 18 hours and washed with 100 mlof 3N hydrochloric acid. The ether solution is dried over magnesiumsulfate and concentrated. The residual oil (14.5 g) is purified by HPLCusing 5% ethyl acetate in cyclohexane as eluent. The first 2.0 L ofeluate gives 8.8 g (19%) of the desired product as an oil, n²⁵ D 1.4567.

Anal Calc'd. for C₁₅ H₁₇ F₄ NO₄ : C, 51.28; H, 4.88; N, 3.99 Found: C,51.39; H, 4.76 ; N, 3.85

EXAMPLE 139 Preparation of dimethyl4-isobutyl-2-methyl-6-(trifluoromethyl) -3,5-pyridinedicarboxylate

To a solution of 8.8 g (0.025 mole) of product of Example 138 in 100 mlof DMF is added 6.0 g (0.16 mole) of sodium borohydride. After 10 min.stirring, the reaction mixture is heated to 65° in 20 min. andmaintained at 65° C. for 11/2 hours before being poured into 500 ml ofwater. The organic is extracted into 500 ml of methylene chloride. Themethylene chloride extract is dried over magnesium sulfate andconcentrated to give 9.9 g of an oil which is purified by HPLC using 10%ethyl acetate in cyclohexane as eluent. The first 2.1 L of eluate givesan oil which is not further identified. The second 1.5 L of eluate gives2.9 g of an oil which is stirred with 2.0 g of DBU and 50 ml of etherfor 4 hours. The ether solution is washed successively with 60 ml of 3 Nhydrochloric acid and 60 ml of water, dried over magnesium sulfate andconcentrated. The residual 2.2 g of an oil is purified by radiallyaccelerated preparatory TLC using 5% ethyl acetate in cyclohexane aseluent. The first fraction gives an oil (1.2 g) which is kugelrohrdistilled at 1 torr (pot temperature 140°) to give 1.1 g (13% yield) ofthe desired product as an oil, nzsD 1.4606.

Anal. Calc'd. for C₁₅ H₁₈ F₃ NO₄ : C, 54.05; H, 5.44; N, 4.20 Found: C,54.06; H, 5.45; N, 4.20.

EXAMPLE 140 Ethyl 6-(difluoromethyl)-5-[[(1-methylethyl)thio]carbonyl]-4-isobutyl-2-(trifluoromethyl)-,3-pyridinecarboxylate

A one liter flask was charged with 32 g (0.08 m) of product of Example16 and 150 ml of ethanol. In a separate flask was stirred 15.84 g (0.24m) of potassium hydroxide (85%) and 75 ml of water. The aqueous solutionwas added to the organic layer and stirring proceeded for 48 hours atroom temperature. The reaction mixture was concentrated, diluted withwater, and extracted with ethyl ether. The aqueous layer was acidifiedwith concentrated HCl, cooled, and extracted with ethyl ether. Theproduct layer was dried over anhydrous MgSO₄ filtered, concentrated anddried under vacuum to yield 24.5 g (82.93%) of acid. The acid wasstirred with 150-200 ml of thionyl chloride and heated at reflux for 24hours. The reaction mixture was concentrated to yield the acid chloridein 84.97% yield.

A 250 ml round bottomed flask was charged with 6.25 g (0.016 m) of theacid chloride, 1.52 g (0.02 m) of propanethiol and 75-100 ml oftetrahydrofuran. To the magnetically stirred mixture was added 2.44 g(0.02 m) of potassium tert-butoxide. The reaction mixture began toevolve heat and was stirred for 30 minutes. The mixture was then pouredinto ice water and extracted with methylene chloride. The organics weredried over anhydrous magnesium sulfate, filtered, and concentrated. Thecrude product was kugelrohr distilled to yield 1.95 g (28.55%). n_(D) ²⁵=1.4704.

Anal. Calc'd. for C₁₈ H₂₂ F₅ N₁ O₃ S₁ : C, 50.58; H, 5.19; Found: C,50.73; H, 5.22; N, 3.24; S, 7.42

EXAMPLE 141 S,S-diethyl2-difluoromethyl)-4-isobutyl-6-(trifluoromethyl)-3,5-pyridinedicarbothioat

A one liter flask was charged with 70.91 g (0.1784 mole) of product ofExample 16 and 300 ml of methanol. In a separate flask was combined93.73 g (1.42 mole) of 85% potassium hydroxide and 150 ml of water. Theaqueous and organic layers were combined and allowed to reflux for 48hours. The reaction mixture was concentrated, diluted with water andextracted with ethyl ether. The ether layer was discarded. The aqueouslayer was acidified with concentrated HCl and the oil precipitate wasextracted with ether. The extract was dried over anhydrous magnesiumsulfate, filtered, and concentrated to yield a viscous liquid (whichlater crystallized) in the amount of 53.7 g (88.22%). To this acid wasadded 250-300 ml of thionyl chloride. The reaction mixture was refluxedfor 24 hours and was concentrated to yield 51.7 g (86.93%) of acidchloride.

A 250 ml flask was charged with 5.66 g (0.0149 mole) of the acidchloride, 75-100 ml of anhydrous tetrahydrofuran, and 5.57 g (0.0898mol) of ethanethiol. To the magnetically stirred mixture was added 3.34g (0.0298 mole) of potassium tert-butoxide. The mixture evolved heat andwas stirred for 45 minutes. The reaction mixture was poured into icewater and stirred. The organics were extracted two times with methylenechloride, washed with ice water, dried over anhydrous magnesium sulfate,concentrated and kugelrohr distilled. The mixture was chromatographedusing 3% ethyl acetate in cyclohexane and concentrated to yield 1.1 g(17.21%) of oil, n_(D) ²⁵ =1.5256.

Anal. Calc'd. for C₁₇ H₂₀ F₅ N₁ O₂ S₂ :C, 47.54; H, 4.69; N, 3.26; S,14.93 Found: C, 47.40; H, 4.88; N, 3.21; S, 14.77

Using procedures similar to those of Examples 140 and 141, otherthioester and dithioester compounds were prepared. These compounds areshown in the following Table 20.

                                      TABLE 20                                    __________________________________________________________________________                                     Analysis                                     Example                                                                            Compound          n.sub.D.sup.25                                                                          Calc'd                                                                            Found                                    __________________________________________________________________________    142  Ethyl 6-(difluoromethyl)-4-propyl                                                               1.4754  C 49.39                                                                             48.93                                         5-[(propylthio)carbonyl]-2-                                                                             H 4.88                                                                              4.64                                          (trifluoromethyl)-3-pyridine-                                                                           N 3.39                                                                              3.38                                          carboxylate               S 7.76                                                                              7.78                                     143  Ethyl 6-(difluoromethyl)-5-[[(1-                                                                1.4723  C 49.39                                                                             49.48                                         methylethyl)thio]carbonyl]-4-                                                                           H 4.88                                                                              4.93                                          propyl-2-(trifluoromethyl)-3-pyridine-                                                                  N 3.39                                                                              3.34                                          carboxylate               S 7.76                                                                              7.85                                     144  Ethyl 6-(difluoromethyl)-5-[[(1,1-                                                              1.4718  C 50.58                                                                             50.43                                         dimethylethyl)thio]carbonyl-]-4-                                                                        H 5.19                                                                              5.21                                          propyl-2-(trifluoromethyl)-3-                                                                           N 3.28                                                                              3.23                                          pyridinecarboxylate                                                      145  Methyl-6-(difluoromethyl)-5-                                                                    1.4788  C 48.12                                                                             48.39                                         [(ethylthio)carbonyl]-4-(2-methyl                                                                       H 4.54                                                                              4.77                                          propyl)-2-(trifluoromethyl)-3-                                                                          N 3.51                                                                              3.32                                          pyridinecarboxylate       S 8.03                                                                              7.73                                     146  S,S-dimethyl 2-(difluoromethyl)-4-                                                              1.4788  C 44.88                                                                             45.44                                         isobutyl-6-trifluoromethyl-                                                                             H 4.02                                                                              4.10                                          3.5-pyridinecarbothioate  N 3.49                                                                              3.47                                                                    S 15.98                                                                             15.99                                    147  S,S-dimethyl 2,6-bis(trifluoro-                                                                 m.p. 63-66° C.                                                                 C 42.96                                                                             43.22                                         methyl)-4-isobutyl-3,5-   H 3.60                                                                              3.79                                          pyridinedicarbothioate    N 3.34                                                                              3.24                                                                    S 15.29                                                                             15.06                                    148  S,S-dimethyl 2,6-bis(trifluoro-                                                                 m.p. 96-98° C.                                                                 C 41.48                                                                             41.30                                         methyl)-4-propyl-3,5-pyridine-                                                                          H 3.23                                                                              3.23                                          dicarbothioate            N 3.46                                                                              3.46                                                                    S 15.82                                                                             15.88                                    149  S,S-diethyl 2,6-bis(trifluoro-                                                                  m.p. 66-69° C.                                                                 C 44.34                                                                             44.29                                         methyl)-4-propyl-3,5-pyridine-                                                                          H 3.95                                                                              3.99                                          dicarbothioate            N 3.23                                                                              3.22                                                                    S 14.79                                                                             14.87                                    __________________________________________________________________________

EXAMPLE 150 3-Ethyl 5-methyl 4-methyl-2-isobutyl -6-(trifluoromethyl)-3,5-pyridinedicarboxylate

An amount of 52.7 g of ethyl 3-amino-4-methyl-2-pentenoate was preparedfrom 98 g ethyl (2-methylpriopionyl) acetate using the procedure ofAberhart and Liv, JOC 1981, 3749. The enamino ester had n_(D) ²⁵=1.4914, bp 92°/6mm. The above enamine (20 g) was mixed in 100 ml THFwith 21.6 g methyl 2,2,2-trifluoroacetoacetate and 6 g of acetaldehyde.Upon adding a couple of drops of piperidine, a spontaneous isotherm to60° was observed. The mixture was then heated with stirring at about 70°(just below reflux) for 11/2 hours. While monitoring with ¹⁹ F nmr, themixture was refluxed for 5 hours, then allowed to stand at roomtemperature overnight. The mixture was stripped of THF to give 46.1 gyield of crude product, 40 g of which was dehydrated using 25 mltrifluoroacetic anhydride and about 100 ml CH₂ Cl₂. An exotherm to 40°was observed, and the material was refluxed for about one hour, thenstripped to give crude product which was kugelrohr distilled(110°-160°/0.15 mm).

4.5 g of this crude intermediate (0.013 mole) was placed in CH₂ Cl₂ and3.4 g of 2,3-dichloro-5,6-dicyano-benzoquinone (DDQ) was added. Thereaction was exothermic. The mixture was stirred for 3 hours at roomtemperature. GLC showed one main peak at the same retention time asstarting material. The product was washed with NaOH/NaHSO₃ to reduceexcess DDQ. The material was stripped of solvent, then kugelrohrdistilled to give 3.5 g of crude product, which was farther purified byHPLC with 3% ethyl acetate, 97% cyclohexane to give a purified fractionwhich was then kugelrohr distilled (bp 140°-150° at 0.15 mm) to give thedesired product: n_(D) ²⁵ 1.4557, 1 g yield.

Anal. Calc'd. for C₁₈ H₂₄ F₃ NO₄ :C, 54.05; H, 5.44; N, 4.20 Found: C,5398; H, 5.48; N, 4.20

EXAMPLE 151 3-Ethyl 5-methyl2-ethyl-4-isobutyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylate

A stirred mixture of 18.0 g (0.20 mole) isovaleraldehyde, 30.8 g (0.20mole) methyl trifluoroacetoacetate, 28.6 g (0.20 mole) ethyl3-amino-2-penteneoate, 60 ml tetrahydrofuran and 3 drops piperidine isheated and held at reflux for 18 hours. The cooled reaction mixture isconcentrated and the residue partially crystallizes on standing atambient temperature. The solids are filtered from an 8.0 g sample,washed with hexane and recrystallized from tetrahydrofuran/hexane togive 1.72 g (22%) white solid, mp 148-150° C.

A stirred mixture of 72 g (0.18 mole) crude solid prepared as above, 30ml (0.21 mole) trifluoroacetic anhydride and 150 ml methylene chlorideis heated and held at reflux for 2 hours. The washed reaction mixture isconcentrated to give 88.0 g oil. To a stirred solution of 43 g (0.09mole) oil in 200 ml methylene chloride cooled with a water bath is addedin portions 17.5 g (0.077 mole)2,3-dichloro-5,6-dicyano-1,4-benzoquinone. The reaction mixture isstirred for 1 hour and filtered. The filtrate is washed twice with 200ml of 20% sodium hydroxide solution. Then with 200 ml 1% hydrochloricacid, dried over magnesium sulfate, filtered and concentrated to give28.2 g oil. Purification by silica gel HPLC of a 10 g sample affordsafter kugelrohr distillation 3.07 g (26%) of light yellow oil, bp105°-110° C./1 mm, n_(D) ²⁵ 1.4582.

Anal. Calc'd. for C₁₇ H₂₂ NF₃ O₄ :C, 56.50; H, 6.14; N, 3.88 Found: C,56.51; H, 6.17; N, 3.84

EXAMPLE 152 Methyl2-(difluorcmethyl)-4-isobutyl-6-(trifluoromethyl)-5-carbethoxy-3-pyridine-N-butylimidate

A mixture of ethyl3-butylcarbamyl-2-(difluoromethyl)-4-isobutyl-6-(trifluoromethyl)-5-pyridinecarboxylateprepared in the same manner as the product of Example 89 in thionylchloride was refluxed overnight. The excess thionyl chloride was removedand the residual oil was kugelrohr distilled at 140° C./0.5 mm to give4.7 g of light yellow liquid (91% yield); n_(D) ²⁵ 1.4668.

To a flame dried 100 ml round bottom flask was placed 30 ml of absolutemethanol. It was blanketed by an atmosphere of nitrogen. To this wasadded 0.63 g (0.0056 mole) of potassium t-butoxide and it was cooled to0° C. To this was added a solution of yellow liquid prepared above (2.5g, 0.0056 mole) in anhydrous ether (20 ml) all at once through a doubletip needle. The mixture turned white and cloudy immediately. It wasstirred at room temperature overnight. The solvent was removed and theresidue was extracted with ether. The ether layer was washed with water,dried (MgSO₄) and concentrated to give 2.49 g of a light yellow oil. Itwas purified by chromatograph using 30% CH₂ Cl₂ in benzene as eluant togive 1.8 g of a light yellow oil (72% yield); n_(D) ²⁵ 1.4546.

Further compounds of the present invention were prepared using thevarious techniques set out in the preceding Examples, sometimes inconjunction with other preparative steps well-known in the art. Thesecompounds are shown in the following Table A, along with certain oftheir physical properties, where available. In Table A the followingabbreviations are used in setting out the various, functional groupssubstituted on the pyridine ring: ##STR47##

                                      TABLE A                                     __________________________________________________________________________    Ex. No.                                                                            R.sub.1                                                                           X       R           Y        R.sub.2                                                                           M.P.     n.sub.D.sup.25             __________________________________________________________________________    153  CF.sub.3                                                                          C(O)OCH.sub.2 CF.sub.3                                                                Cycpr       C(O)OCH.sub.2 CF.sub.3                                                                 CHF.sub.2                                                                         44-46                               154  CF.sub.3                                                                          C(O)SPr CH.sub.2 CHMe.sub.2                                                                       C(O)SPr  CHF.sub.2    1.4978                     155  CF.sub.3                                                                          C(O)OMe CH.sub.2 CHMe.sub.2                                                                       C(O)O    CHF.sub.2                                                                         148-150                                                          NH(CH.sub.3).sub.2                               156  CF.sub.3                                                                          C(O)OMe CHCH.sub.2  C(O)OMe  CHF.sub.2                                                                         b.p. 100-105/                                                                 0.1 torr                            157  CF.sub.3                                                                          C(O)OEt CH.sub.2 S(O)Me                                                                           C(O)OMe  CHF.sub.2                                                                         75-76                               158  CF.sub.3                                                                          C(O)OEt CH.sub.2 SMe                                                                              C(O)OH   CHF.sub.2                                                                         88-89                               159  CF.sub.3                                                                          C(O)OEt 2(Thiole)   C(O)OEt  CHF.sub.2                                                                         38-40                               160  CF.sub.3                                                                          C(O)OEt 2(Thiole)   C(O)OH   CHF.sub.2                                                                         129.5-131                           161  CF.sub.3                                                                          C(O)OEt 2(Thiole)   C(O)OMe  CHF.sub.2    1.4998                     162  CF.sub.3                                                                          C(O)OEt CH.sub.2 SEt                                                                              C(O)OMe  CHF.sub.2    1.4749                     163  CF.sub.3                                                                          C(O)OEt CHMeSMe     C(O)OMe  CHF.sub.2    1.4734                     164  CF.sub.3                                                                          C(O)OEt 2(Thiole)   C(O)OEt  CH.sub.3     1.5078                     165  CF.sub.3                                                                          C(O)OEt CH.sub.3    C(O)OMe  CH.sub.3     1.4591                     166  CF.sub.3                                                                          C(O)OEt CH.sub.2 Cypor                                                                            C(O)OEt  CHF.sub.2                                                                         b.p.                                                                          125-130/0.5 mm                      167  CF.sub.3                                                                          C(O)OMe CH2CHMe2    C(O)NHMe CHF2                                                                              185-188                             168  CF.sub.3                                                                          C(O)OEt CH.sub.2 CHMe.sub.2                                                                       C(O)NHMe CHF.sub.2                                                                         108-110                             169  CF.sub.3                                                                          C(O)OEt CHEtSMe     C(O)OMe  CHF.sub.2    1.4731                     170  CF.sub.3                                                                          C(O)OEt CMe.sub.2 SMe                                                                             C(O)OMe  CHF.sub.2    1.4848                     171  CF.sub.3                                                                          C(O)OEt CH.sub.2 CHMe.sub.2                                                                       C(O)OEt  CH.sub.3     1.4582                     172  CF.sub.3                                                                          C(O)OEt CH.sub.2 CHMe.sub.2                                                                       C(O)OMe  CH.sub.3     1.4595                     173  CF.sub.3                                                                          C(O)OMe CH.sub.2 CHMe.sub.2                                                                       C(O)OEt  CH.sub.3     1.4590                     174  CF.sub.3                                                                          C(O)OEt CHMeOMe     C(O)OMe  CHF.sub.2    1.4473                     175  CF.sub.3                                                                          C(O)OEt CH.sub.2 CH.sub.2 CN                                                                      C(O)OMe  CHF.sub.2                                                                           95-96.5                           176  CF.sub.3                                                                          C(O)OEt CH.sub.2 -1-                                                                              C(O)OMe  CHF.sub.2                                                                         73-74                                                Aziridine                                                    177  CF.sub.3                                                                          C(O)OEt CHMe.sub.2  C(O)OEt  CH.sub.3     1.4588                     178  CF.sub.3                                                                          C(O)OEt CHMe.sub.2  C(O)OMe  CH.sub.3     1.4608                     179  CF.sub.3                                                                          C(O)OEt CHMeEt      C(O)OEt  CH.sub.3     1.4586                     180  CF.sub.3                                                                          C(O)OEt CHMeEt      C(O)OMe  CH.sub.3     1.4508                     181  CF.sub.3                                                                          C(O)OEt CHCHNMe.sub.2                                                                             C(O)OEt  CHF.sub.2                                                                         b.p. 160-                                                                     180/0.10-0.15 torr                  182  CF.sub.3                                                                          C(O)OEt CMeCHNMe.sub.2                                                                            C(O)OEt  CHF.sub.2                                                                         b.p. 150/0.5 torr                   183  CF.sub.3                                                                          C(O)OEt CH.sub.2 C(O)H                                                                            C(O)OMe  CHF.sub.2                                                                         81-82                               184  CF.sub.3                                                                          C(O)OMe CH.sub.2 CH(OMe).sub.2                                                                    C(O)OMe  CHF.sub.2                                                                         44-45                               185  CF.sub.3                                                                          C(O)OEt CH.sub.2 C(O)H                                                                            C(O)OEt  CHF.sub.2                                                                         53-55                               186  CF.sub.3                                                                          C(O)OEt CHMeC(O)OMe C(O)OMe  CHF.sub.2                                                                         56.5-58                             187  CF.sub.3                                                                          C(O)OEt CH2C(O)OH   C(O)OH   CHF.sub.2                                                                         176-177                             188  CF.sub.3                                                                          C(O)OEt CH.sub.2 Me C(O)OEt  CH.sub.3     1.5020                     189  CF.sub.3                                                                          C(O)OMe CH.sub.2 CHMe.sub.2                                                                       C(O)OCH.sub.2 Cypor                                                                    CHF.sub.2    1.4578                     190  CF.sub.3                                                                          C(O)OMe CH.sub.2 Pr C(O)OMe  CHF.sub.2    1.4458                     191  CF.sub.3                                                                          C(O)OEt CH.sub.2 CHMe.sub.2                                                                       C(O)SPr  CHF.sub.2    1.472                      192  CF.sub.3                                                                          C(O)OEt CH.sub.2 CHMe.sub.2                                                                       C(O)NHBu CHF.sub.2                                                                         69-71                               193  CF.sub.3                                                                          C(O)OEt CH.sub.2 CHMe.sub.2                                                                       C(O)OCH.sub.2                                                                          CHF.sub.2    1.4531                                                  Cycpr                                            194  CF.sub.3                                                                          C(O)OEt CH.sub.2 CHMe.sub.2                                                                       C(O)SMe  CHF.sub.2    1.4759                     195  CF.sub.3                                                                          C(O)OEt CHMe.sub.2  C(O)SMe  CHF.sub.2    1.4808                     196  CF.sub.3                                                                          C(O)OEt CHMe.sub.2  C(O)SEt  CHF.sub.2    1.4783                     197  CF.sub.3                                                                          C(O)OEt CH.sub.2 Cycpr                                                                            C(O)OH   CHF.sub.2                                                                          96-100                             198  CF.sub.3                                                                          C(O)OMe CH.sub.2 Cycpr                                                                            C(O)OMe  CHF.sub.2    1.4625                     199  CF.sub.3                                                                          C(O)OEt CH.sub.2 Cycpr                                                                            C(O)OMe  CHF.sub.2    1.4595                     200  CF.sub.3                                                                          C(O)OCH.sub.2 CN                                                                      CH.sub.2 CHMe.sub.2                                                                       C(O)OCH.sub.2 CN                                                                       CHF.sub.2                                                                            88-90° C.                 201  CF.sub.3                                                                          C(O)OEt CH.sub.2 CHMeCF.sub.3                                                                     C(O)OEt  CHF.sub.2                                                                         30-32                               202  CF.sub.3                                                                          C(O)OH  CH.sub.2 CHMeCF.sub.3                                                                     C(O)OH   CHF.sub.2                                                                         205-207                             203  CF.sub.3                                                                          C(O)OMe CH.sub.2 CHMeCF.sub.3                                                                     C(O)OMe  CHF.sub.2                                                                         68-70                               204  CF.sub.3                                                                          C(O)OEt CH.sub.2 CHMe.sub.2                                                                       C(NBu)Cl CHF.sub.2    1.4668                     205  CF.sub.3                                                                          C(O)OEt CH.sub.2 CHMe.sub.2                                                                       C(NBu)OMe                                                                              CHF.sub.2    1.4546                     206  CF.sub.3                                                                          CN      CH.sub.2 CHMe.sub.2                                                                       CN       CHF.sub.2                                                                         39-41                               207  CF.sub.3                                                                          C(O)SMe CH.sub.2 Cycpr                                                                            C(O)SMe  CHF.sub.2                                                                         80-83                               208  CF.sub.3                                                                          C(O)OMe CH2Cycpr    C(O)SMe  CHF.sub.2    1.4925                     209  CF.sub.3                                                                          C(O)OMe CHMeSMe     C(O)OMe  CHF.sub.2                                                                         59-62                               210  CF.sub.3                                                                          C(O)OMe CMe.sub.2 SMe                                                                             C(O)OMe  CHF.sub.2                                                                         56-69                               211  CF.sub.3                                                                          C(O)OMe CHMeSMe     C(O)OEt  CHF.sub.2    1.4730                     212  CF.sub.3                                                                          C(O)OMe CMe.sub.2 SMe                                                                             C(O)OEt  CHF.sub.2    1.4847                     213  CF.sub.3                                                                          C(O)OMe CH.sub.2 CHMe.sub.2                                                                       C(O)OMe  CF.sub.3                                                                          80.5-82.5                           214  CF.sub.3                                                                          C(O)OEt CH.sub.3    C(O)OEt  CH.sub.3     1.4552                     215  CH.sub.3                                                                          C(O)OEt CH.sub.2 CHMe.sub.2                                                                       C(O)OEt  CHF.sub.2    1.4745                     216  CHF.sub.2                                                                         C(O)OEt CH.sub.3    C(O)OEt  CH.sub.3     1.4752                     217  CF.sub.3                                                                          C(O)OMe CH.sub.2 CHCHC(O)OET                                                                      C(O)OMe  CHF.sub.2    1.4644                                      (cis)                                                        218  CF.sub.3                                                                          C(O)OMe CH.sub.3    C(O)OMe  CHF.sub.2                                                                         37-40                               219  CF.sub.3                                                                          C(O)OMe CH.sub.2 C(O)NH.sub.2                                                                     C(O)OMe  CHF.sub.2                                                                         160-163                             220  CF.sub.3                                                                          C(O)OMe CH.sub.2 C(O)OH                                                                           C(O)OMe  CHF.sub.2                                                                         156-157                             221  CF.sub.3                                                                          C(O)OMe CH.sub.2 CN C(O)OMe  CHF.sub.2                                                                         137-139                             222  CF.sub.3                                                                          C(O)OMe CH.sub.2 -2-(1,3-di-                                                                      C(O)OMe  CHF.sub.2                                                                         103-106                                              thiolane)                                                    223  CF.sub.3                                                                          C(O)OMe CH.sub.2 C(O)NHCMe.sub.2                                                                  C(O)OMe  CHF.sub.2                                                                         132-133                                              CH.sub.2 OH                                                  224  CF.sub.3                                                                          C(O)OMe CH.sub.2 C(O)NHCMe.sub.2                                                                  C(O)OMe  CHF.sub.2                                                                         136-137                                              CH.sub.2 Cl                                                  225  CF.sub.3                                                                          C(O)Me  CH.sub.2 C(O)SCHMe.sub.2                                                                  C(O)OMe  CHF.sub.2                                                                         69-70                               226  CF.sub.3                                                                          C(O)OMe CH.sub.2 C(O)OEt                                                                          C(O)OMe  CHF.sub.2                                                                         81-82                               227  CF.sub.3                                                                          C(O)OMe CH.sub.2 C(O)NMe.sub.2                                                                    C(O)OMe  CHF.sub.2                                                                           137-138.5                         228  CF.sub.3                                                                          C(O)OMe CH.sub.2 CHMe.sub.2                                                                       C(O)SMe  CHF.sub.2                                                                         36-40                               229  CF.sub.3                                                                          C(O)OMe CH.sub.2 CHMe.sub.2                                                                       C(O)SCHMe.sub.2                                                                        CHF.sub.2    1.4752                     230  CF.sub.3                                                                          C(O)SMe CH.sub.2 Pr C(O)SMe  CHF.sub.2                                                                         68-71                               231  CF.sub.3                                                                          C(O)SMe CHMe.sub.2  C(O)SMe  CHF.sub.2                                                                         96-98                               232  CF.sub.3                                                                          C(O)SEt CHMe.sub.2  C(O)SEt  CHF.sub.2                                                                         58-62                               233  CF.sub.3                                                                          C(O)OMe CH.sub.2 CHMe.sub.2                                                                       C(O)OCHMe.sub.2                                                                        CHF.sub.2    1.4467                     234  CF.sub.3                                                                          C(O)SEt CH.sub.2 Pr C(O)SEt  CHF.sub.2                                                                         32-34    1.5420                     235  CF.sub.3                                                                          C(O)OMe CH.sub.2 CHMe.sub.2                                                                       C(O)SPr  CHF.sub.2    1.4780                     236  CF.sub.3                                                                          C(O)SEt CH.sub.2 CHMe.sub.2                                                                       C(O)SEt  CF.sub.3                                                                          34-37                               237  CF.sub.3                                                                          C(O)OMe Cycpr       C(O)SMe  CHF.sub.2                                                                         68-71                               238  CF.sub.3                                                                          C(O)OMe Cycpr       C(O)SEt  CHF.sub.2                                                                         51-53                               239  CH.sub.2 F                                                                        C(O)OMe CH.sub.2 CHMe.sub.2                                                                       C(O)OMe  CH.sub.3     1.4909                     240  CH.sub. 2 F                                                                       C(O)OMe CH.sub.2 Me C(O)OMe  CH.sub.3                                241  CHF.sub.2                                                                         C(O)OMe CH.sub.2 CHMe.sub.2                                                                       C(O)OMe  CH.sub.3     1.4795                     242  CF.sub.3                                                                          C(O)OEt CF.sub.3    C(O)OEt  CHF.sub.2    1.4191                     243  CF.sub.3                                                                          C(O)OEt CHF.sub.2   C(O)OEt  CF.sub.3                                                                          50.5-52.5                           244  CF.sub.3                                                                          C(O)OEt CH.sub.2 SMe                                                                              C(O)OMe  CH.sub.3     1.4904                     245  CF.sub.3                                                                          C(O)OMe CH.sub.2 SMe                                                                              C(O)OMe  CH.sub.3     1.4951                     246  CH.sub.2 F                                                                        C(O)OEt CH.sub.2 CHMe.sub.2                                                                       C(O)OEt  CH.sub.3     1.4849                     __________________________________________________________________________

As noted above, the compounds of this invention have been found to beeffective as herbicides, particularly as pre-emergent herbicides. Tables20 and 21 summarize results of tests conducted to determine thepre-emergent herbicidal activity of the compounds of this invention.

The pre-emergent tests are conducted as follows:

A good grade of top soil is placed in aluminum pans and compacted to adepth of 0.95 to 1.27 cm. from the top of the pan. 0n the top of thesoil is placed a predetermined number of seeds or vegetative propagulesof various plant species. The soil required to level fill the pans afterseeding or adding vegetative propagules is weighed into a pan. A knownamount of the active ingredient applied in acetone as a solvent isthoroughly mixed with the soil, and the herbicide/soil mixture is usedas a cover layer for prepared pans. In Table I below the amount ofactive ingredient is equal to the rate of 11.2 kg/ha. After treatment,the pans are moved into a greenhouse bench where they are watered frombelow as needed to give adequate moisture for germination and growth.

Approximately 10-14 days (usually 11 days) after treating, the plantsare observed and the results recorded. In some instances an additionalobservation was made 24-28 days (usually 25 days) after treating, andthese observations are denoted in the Tables by an asterisk (*)following the "Example" column. Table I below summarizes such results.The herbicidal rating is obtained by means of a fixed scale based on thepercent of each plant species.

The ratings are defined as follows:

    ______________________________________                                               % Inhibition                                                                           Rating                                                        ______________________________________                                                0-24    0                                                                    24-49    1                                                                    50-74    2                                                                     75-100  3                                                             ______________________________________                                    

The plant species utilizing in one set of tests, the data for which areshown in Table 20, are identified by letter in accordance with thefollowing legend:

    ______________________________________                                        A       Canada Thistle*                                                                              E     Lambsquarters                                    B       Cocklebur      F     Smartweed                                        C       Velvetleaf     G     Yellow Nutsedge*                                 D       Morning Glory  H     Quackgrass*                                                I   Johnsongrass*                                                             J   Downy Brome                                                               K   Barnyardgrass                                                   ______________________________________                                         *Grown from vegetative propagules                                        

                  TABLE 21                                                        ______________________________________                                        Example                                                                                                    No. kg/h A B C D E F G H I J K                   ______________________________________                                         6     11.2   3     1   3   3    3   3   0   3   1   3                                                     3                                                                               6* 11.2 3 0 3 3 3 3 0 3 1 3 3                                                7 11.2 2 2 3 3 2 0 3 0 3 3                                                    94 11.2 1 0 2 2 3 3 1 3 0 3 3                                                 95 11.2 1 0 2 3 3 2 0 3 0 3 3                                                 12 11.2 3 2 3 3 3 3 3 3 3 3 3                                                 38 11.2 0 0 0 0 0 0 0 0 0 0 0                                                 32 11.2 3 1 3 3 3 3 3 3 3 3 3                                                 37 11.2 3 0 3 3 3 3 1 3 0 3 3                                                 13 11.2 3 1 3 3 3 3 3 3 3 3 3                                                 39 11.2 0 0 0 0 0 0 0 0 0 0 0                                                 28 11.2 0 0 0 0 0 0 0 0 0 0 0                                                 96 11.2 -- 0 0 1 3 -- 0 0 0 3 3                                               19 11.2 -- 0 0 0 0 0 0 0 0 0 1                                                8 11.2 0 0 0 0 1 1 0 0 0 0 3                                                  46 11.2 0 0 0 0 3 0 0 0 0 0 3                                                 61 11.2 3 1 3 3 3 3 1 3 1 3 3                                                 45 11.2 0 0 0 0 0 0 0 0 0 0 0                                                 88 11.2 0 0 0 0 0 -- 0 0 0 0 0                                                92 11.2 3 0 1 3 2 -- 0 3 3 3 3                                                89 11.2 0 0 0 0 3 -- 0 0 0 0 3                                                27 11.2 -- 0 1 3 3 -- 0 3 3 3 3                                               59 11.2 -- 1 3 3 3 -- 3 3 3 3 3                                               59* 11.2 -- 1 3 3 3 -- 3 3 3 3 3                                              60 11.2 -- 0 0 1 3 -- 0 1 1 3 3                                               91 11.2 -- 0 0 0 0 -- 0 0 0 0 1                                               52 11.2 -- 3 3 3 3 -- 3 3 3 3 3                                               52* 11.2 -- 3 3 3 3 -- 3 3 3 3 3                                              58 11.2 -- 0 0 0 0 0 0 0 0 1 1                                                62 11.2 -- 0 2 3 3 3 0 2 0 3 3                                                90 11.2 -- 0 1 2 1 1 0 0 0 3 3                                                18 11.2 -- 1 3 3 3 3 2 3 3 3 3                                                40 11.2 -- 0 0 0 0 0 0 0 0 0 0                                                29 11.2 -- 0 0 1 1 1 0 3 0 2 3                                                47 11.2 -- 0 1 2 3 2 0 0 0 2 3                                                48 11.2 -- 0 0 0 0 0 0 0 0 0 0                                                46 11.2 -- 0 2 3 3 3 0 3 3 3 3                                                15 11.2 3 2 3 3 3 3 3 3 3 3 3                                                 44 11.2 3 0 2 3 3 3 0 1 0 3 3                                                 31 11.2 3 1 2 3 3 3 0 0 0 3 3                                                 53 11.2 3 2 3 3 3 3 3 3 3 3 3                                                 16 11.2 3 2 3 3 3 3 2 3 3 3 3                                                 21 11.2 1 0 0 2 3 3 0 0 3 3 3                                                 64 11.2 3 0 3 3 3 3 1 3 2 3 3                                                 32 11.2 0 0 0 0 0 0 0 0 0 0 1                                                 54 11.2 3 3 3 3 3 3 3 3 3 3 3                                                 54* 11.2 3 3 3 3 3 3 3 3 3 3 3                                                37 11.2 0 0 0 0 0 0 0 0 0 0 0                                                 11 11.2 3 0 3 3 3 -- 0 3 3 3 3                                                87 11.2 3 0 3 3 3 -- 3 3 3 3 3                                                97 11.2 0 0 1 1 1 2 0 0 1 3 3                                                 20 11.2 3 0 3 2 3 -- 0 3 1 3 3                                                41 11.2 0 0 0 0 0 -- 0 0 0 0 0                                                22 11.2 0 0 1 2 3 -- 0 0 0 3 3                                                75 11.2 0 0 3 3 3 -- 0 3 1 3 3                                                14 11.2 3 3 3 3 3 -- 3 3 3 3 3                                                30 11.2 0 0 0 0 0 -- 0 0 0 0 0                                                23 11.2 0 0 0 2 3 -- 0 0 0 3 3                                                35 11.2 1 0 0 0 2 -- 0 0 0 0 3                                                17 11.2 3 2 3 3 3 -- 2 3 3 3 3                                                34 11.2 1 1 0 1 0 -- 0 0 0 1 3                                                50 11.2 0 0 3 3 3 -- 0 0 0 2 3                                                55 11.2 3 2 3 3 3 -- 3 3 3 3 3                                                55* 11.2 3 3 3 3 3 -- 3 3 3 3 3                                               33 11.2 0 0 0 0 0 -- 0 0 0 0 0                                                49 11.2 0 0 0 -- 0 -- 0 0 0 0 0                                               65 11.2 0 0 3 3 3 -- 0 3 2 3 3                                                51 11.2 0 0 0 0 0 0 0 0 0 0 0                                                 68 11.2 0 0 0 0 1 2 0 0 0 3 3                                                 67 11.2 3 2 3 3 3 3 3 3 3 3 3                                                 76 11.2 0 0 0 0 0 0 0 0 0 0 0                                                 77 11.2 0 0 0 1 0 0 0 0 0 0 0                                                 83 11 2 0 0 0 0 0 0 0 0 0 0 0                                                  82 11.2 1 0 0 0 0 0 0 0 0 0 3                                                84 11.2 3 1 3 3 3 3 0 3 3 3 3                                                 66 11.2 0 0 1 0 0 0 0 0 0 1 1                                                 85 11.2 3 3 3 3 3 3 3 3 3 3 3                                                 86 11.2 3 1 3 3 3 3 3 3 3 3 3                                                112 11.2 0 0 3 2 3 3 1 0 0 3 3                                                 70 11.2 0 0 1 3 3 -- 0 2 0 3 3                                                24 11.2 3 0 3 3 3 -- 2 3 0 3 3                                                36 11.2 0 0 0 0 0 0 0 0 0 0 0                                                 71 11.2 3 0 3 3 3 3 0 3 1 3 3                                                103 11.2 1 0 2 3 3 3 0 2 0 3 3                                                100 11.2 0 0 0 0 0 0 0 0 0 0 0                                                 69 11.2 3 3 3 3 3 -- 3 3 3 3 3                                                72 11.2 3 2 3 3 3 -- 3 3 3 3 3                                                99 11.2 3 0 3 0 3 3 0 1 0 0 1                                                 81 11.2 3 0 3 3 3 3 2 3 3 3 3                                                 42 11.2 0 1 0 0 3 0 1 0 0 0 3                                                 74 11.2 3 0 3 3 3 3 0 3 0 3 3                                                 78 11.2 -- 0 0 0 0 0 0 0 0 0 0                                                73 11.2 3 1 3 3 3 3 1 3 0 3 3                                                 98 11.2 0 0 0 0 0 0 0 0 0 0 0                                                 10 11.2 3 0 2 3 3 3 2 3 1 3 3                                                101 11.2 3 3 3 3 3 3 3 3 1 3 3                                                 25 11.2 3 3 3 3 3 3 3 3 3 3 3                                                102 11.2 0 -- 2 0 3 3 0 0 0 1 1                                               134 11.2 3 1 3 3 3 3 3 3 3 3 3                                                130 11.2 1 0 3 0 3 3 1 0 0 1 3                                                128 11.2 0 0 0 0 3 1 0 0 0 0 1                                                104 11.2 1 0 3 3 3 3 1 3 0 3 3                                                127 11.2 0 0 3 3 3 3 1 3 0 3 3                                                129 11.2 3 2 3 3 3 3 1 3 3 3 3                                                131 11.2 3 3 3 3 3 3 3 3 3 3 3                                                105 11.2 3 0 3 3 3 3 2 3 1 3 3                                                133 11.2 3 3 3 3 3 3 3 3 3 3 3                                                 80 11.2 3 2 3 3 3 3 3 3 3 3 3                                                 79 11.2 0 0 0 0 0 0 0 0 0 0 0                                                 26 11.2 3 0 3 3 3 3 2 3 3 3 3                                                 27 11.2 1 0 2 2 3 3 0 1 0 3 3                                                123 11.2 3 2 3 3 3 3 3 3 3 3 3                                                124 11.2 3 0 3 3 3 3 2 3 2 3 3                                                119 11.2 0 0 0 0 0 0 0 0 0 0 0                                                109 11.2 0 0 0 0 0 0 0 0 0 3 3                                                 43 11.2 0 0 0 0 0 0 0 0 0 0 0                                                107 11.2 0 0 0 0 0 0 0 0 0 0 0                                                110 11.2 3 0 3 2 3 3 2 3 3 3 3                                                111 11.2 3 1 3 3 3 3 3 3 3 3 3                                                106 11.2 0 0 0 0 0 0 0 0 0 0 0                                                120 11.2 0 0 0 0 0 0 0 0 0 0 0                                                122 11.2 3 1 3 3 3 3 3 3 3 3 3                                                117 11.2 3 3 3 3 3 3 3 3 3 3 3                                                118 11.2 0 0 0 0 0 0 0 0 0 0 0                                                113 11.2 3 1 2 2 3 3 1 0 0 3 3                                                121 11.2 0 0 0 0 1 0 0 0 0 0 0                                                125 11.2 3 1 3 3 3 3 3 3 3 3 3                                                137 11.2 3 0 3 3 3 3 1 3 1 3 3                                                136 11.2 3 2 3 3 3 3 1 3 3 3 3                                                121 11.2 0 0 0 0 1 0 0 0 0 0 0                                                125 11.2 3 1 3 3 3 3 3 3 3 3 3                                                137 11.2 3 0 3 3 3 3 1 3 1 3 3                                                136 11.2 3 2 3 3 3 3 1 3 3 3 3                                                135 11.2 1 0 0 0 0 0 1 0 0 0 3                                                138 11.2 3 3 3 3 3 3 3 3 3 3 3                                                139 11.2 3 3 3 3 3 3 3 3 3 3 3                                                140 11.2 2 0 0 0 3 3 0 1 0 3 3                                                141 11.2 3 0 3 2 3 3 0 3 3 3 3                                                142 11.2 3 0 3 3 3 3 0 3 0 3 3                                                143 11.2 0 0 1 0 2 1 0 1 0 3 3                                                144 11.2 3 0 1 0 0 0 0 0 3 0 3                                                145 11.2 3 3 3 3 3 3 1 3 3 3 3                                                146 11.2 3 3 3 3 3 3 3 3 3 3 3                                                147 11.2 3 3 3 3 3 3 3 3 3 3 3                                                148 11.2 3 3 3 3 3 3 3 3 3 3 3                                                149 11.2 0 0 0 0 3 3 0 0 0 3 3                                                150 11.2 3 3 3 3 3 3 3 3 3 3 3                                                151 11.2 N 3 3  33 3 3 3 3 3 3 3                                              152 11.2 0 N 0 1 1 3 0 2 0 3 3                                                153 11.2 0 0 2 2 3 3 0 0 1 3 3                                                154 11.2 0 0 0 0 0 0 0 0 0 0 0                                                155 11.2 1 0 0 0 0 0 0 0 0 0 0                                                156 11.2 0 3 0 1 1 1 0 0 0 0 1                                                157 11.2 3 0 1 2 3 3 0 3 1 0 3                                                158 11.2 1 0 0 0 2 0 1 0 0 0 3                                                159 11.2 0 1 3 3 3 3 0 0 1 3 3                                                160 11.2 0 0 0 0 0 0 0 0 0 0 1                                                161 11.2 3 0 3 3 3 3 0 3 1 3 3                                                162 11.2 3 0 3 3 3 3 0 2 0 3 3                                                163 11.2 3 1 3 3 3 3 3 3 3 3 3                                                164 11.2 1 0 1 3 3 3 0 0 0 1 3                                                165 11.2 0 0 2 3 2 2 0 3 3 3 3                                                166 11.2 3 3 3 3 3 3 3 3 -- 3 3                                               167 11.2 1 2 2 2 3 3 0 1 0 3 3                                                168 11.2 3 N 3 3 3 3 1 2 1 3 3                                                169 11.2 3 1 3 3 3 3 1 3 0 3 3                                                170 11.2 3 1 3 3 3 3 1 3 3 3 3                                                171 11.2 3 2 3 3 3 3 1 3 3 3 3                                                172 11.2 3 3 3 3 3 3 3 3 3 3 3                                                173 11.2 3 2 3 3 3 3 3 3 3 3 3                                                174 11.2 3 0 3 3 3 3 0 3 1 3 3                                                175 11.2 3 1 3 3 3 3 1 3 0 3 3                                                176 11.2 0 0 1 1 1 2 0 1 -- 1 3                                               177 11.2 3 1 3 3 3 3 0 3 -- 3 3                                               178 11.2 3 0 3 3 3 3 1 3 3 3 3                                                179 11.2 3 0 2 2 3 3 0 2 3 3 3                                                180 11.2 3 0 3 3 3 3 1 3 3 3 3                                                181 11.2 0 0 0 0 0 1 0 0 0 1 3                                                182 11.2 0 0 2 0 0 0 0 0 0 3 2                                                183 11.2 0 0 0 0 0 0 0 0 -- 0 0                                               184 11.2 1 0 2 3 1 2 0 3 -- 3 3                                               185 11.2 0 0 0 0 0 0 0 0 -- 0 0                                               186 11.2 3 1 3 3 3 3 0 0 -- 3 3                                               187 11.2 N 0 0 0 3 0 0 1 N 3 0                                                188 11.2 3 N 3 3 3 3 3 3 3 3 3                                                189 11.2 N 0 0 0 3 2 0 0 N 0 3                                                190 11.2 3 1 3 3 3 3 2 3 -- 3 3                                               191 11.2 0 0 2 0 0 3 0 0 -- 3 3                                               192 11.2 1 1 0 0 1 1 0 0 N 1 3                                                193 11.2 0 3 2 3 3 3 0 1 3 3 3                                                194 11.2 3 3 3 3 3 3 3 3 3 3 3                                                195 11.2 3 3 3 3 3 3 3 3 3 3 3                                                196 11.2 3 3 3 3 3 3 1 3 0 3 3                                                197 11.2 N 0 0 0 0 0 0 0 -- 0 0                                               198 11.2 3 3 3 3 3 3 3 3 N 3 3                                                199 11.2 3 3 3 3 3 3 3 3 N 3 3                                                200 11.2 1 1 3 3 3 3 0 0 -- 3 3                                               201 11.2 3 1 3 3 3 3 0 3 3 3 3                                                202 11.2 1 0 0 0 0 0 0 0 N 0 0                                                203 11.2 3 1 3 3 3 3 2 3 3 3 3                                                204 11.2 0 N 0 0 0 1 0 0 0 1 3                                                205 11.2 0 N 0 1 1 3 0 2 0 3 3                                                206 11.2 3 N 2 1 1 3 1 0 0 0 0                                                207 11.2 3 N 3 3 3 3 3 3 2 3 3                                                208 11.2 3 3 3 3 3 3 3 3 3 3 3                                                209 11.2 3 3 3 3 3 3 2 3 3 3 3                                                210 11.2 3 3 3 3 3 3 2 3 2 3 3                                                211 11.2 3 3 3 3 3 3 3 3 3 3 3                                                212 11.2 3 N 3 3 3 3 1 3 1 3 3                                                213 11.2 3 3 3 3 3 3 3 3 3 3 3                                                215 11.2 3 1 3 3 3 3 0 3 3 3 3                                                216 11.2 0 3 1 1 3 1 0 0 0 0 3                                                217 11.2 0 0 0 0 0 0 0 0 N 0 0                                                219 11.2 0 0 0 0 0 0 0 0 0 0 0                                                220 11.2 0 1 0 0 0 0 0 0 0 0 0                                                221 11.2 0 0 0 0 2 1 0 0 0 0 3                                                222 11.2 0 0 0 0 0 0 0 0 0 0 0                                                223 11.2 0 0 0 0 0 0 0 0 0 0 0                                                224 11.2 0 0 0 0 0 0 0 0 0 0 0                                                225 11.2 N 0 0 0 0 0 0 0 0 0 2                                                226 11.2 N 0 0 0 0 0 0 0 0 0 0                                                227 11.2 N 0 0 0 0 0 0 1 0 0 0                                                233 11.2 3 2 3 3 3 3 2 3 3 3 3                                                234 11.2 3 1 1 3 3 3 0 0 0 2 3                                                235 11.2 3 1 3 3 3 3 0 0 3 3 3                                                236 11.2 3 0 3 3 3 3 0 3 1 3 3                                                237 11.2 N 1 3 3 3 3 3 3 0 3 3                                                238 11.2 N 2 3 3 3 3 0 3 3 3 3                                                239 11.2 1 1 3 3 3 3 2 3 3 3 3                                                240 11.2 0 0 0 0 3 2 0 0 1 0 3                                                241 11.2 3 1 3 3 3 3 3 3 3 3 3                                                242 11.2 2 1 3 3 3 3 0 3 1 3 3                                                243 11.2 3 1 3 3 3 3 0 3 1 3 3                                                244 11.2 3 3 3 3 3 3 3 3 1 3 3                                                245 11.2 N 0 3 3 3 3 3 3 3 3 3                                                246 11.2 N 3 3 3 3 3 2 0 0 3 3                   ______________________________________                                    

The compounds were further tested by utilizing the above procedure onthe following plant species:

    ______________________________________                                        L       Soybean        R       Hemp Sesbania                                  M       Sugarbeet      E       Lambsquarters                                  N       Wheat          F       Smartweed                                      O       Rice           C       Velvetleaf                                     P       Sorghum        J       Downy Brome                                    B       Cocklebur      S       Panicum                                        Q       Wild Buckwheat K       Barnyardgrass                                  D       Morning Glory  T       Crabgrass                                      ______________________________________                                    

The results are summarized in Table 22.

                                      TABLE 22                                    __________________________________________________________________________    Example No.                                                                          kg/h L M N O P B Q D R E F C J S K T                                   __________________________________________________________________________    2      .056 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 --                                         .28  0 0 0 0 0 3 0 0 0 0 0 0 0 0 0 --                                         1.12 0 1 0 0 0 0 0 0 3 1 1 3 0 0 0 --                                         5.6  0 1 3 3 3 1 1 3 3 2 2 2 3 3 3 --                                         11.2 2 2 3 3 3 0 3 3 3 3 2 1 3 3 3 --                                  4      .28  --                                                                              0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                          1.12 --                                                                              0 0 0 0 0 1 0 3 0 --                                                                              1 0 0 0 3                                          5.6  --                                                                              3 3 2 3 0 2 2 0 3 --                                                                              3 3 3 3 3                                   5      .28  --                                                                              0 0 0 0 0 0 0 3 3 --                                                                              0 0 0 0 1                                          1.12 --                                                                              0 0 0 0 0 1 0 2 0 --                                                                              0 0 0 0 1                                          5.6  --                                                                              1 0 0 0 0 0 0 1 2 --                                                                              0 3 2 3 3                                   9      1.12 --                                                                              0 0 0 0 0 2 0 3 0 --                                                                              0 1 0 0 0                                          5.6  --                                                                              0 0 0 0 0 0 0 0 2 --                                                                              0 1 2 3 3                                   1      .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 1 1 1 2 1 0 0 1 2 2 0 0 1 2 3 3                                          5.6  3 3 3 3 3 0 2 3 2 3 3 1 3 3 3 3                                   6      .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 0 1 1 1 1 0 0 0 1 0 0 0 0 2 3 3                                          5.6  3 3 3 3 3 1 3 3 3 3 2 1 3 3 3 3                                   7      .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .28  0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 3                                          1.12 0 1 3 3 0 0 0 0 0 1 1 0 1 1 2 3                                               0 1 3 2 0 0 0 0 0 3 1 0 1 1 2 3                                          5.6  3 3 3 3 3 0 2 3 3 3 3 1 3 3 3 3                                               3 3 3 3 3 0 0 3 3 3 3 1 3 3 3 3                                   94     .056 0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 1                                          1.12 0 1 0 1 0 0 0 0 0 1 --                                                                              0 0 0 1 2                                          5.6  0 2 3 2 2 0 0 0 1 3 3 1 2 3 3 3                                   95     .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2                                          5.6  0 1 2 1 1 0 0 1 1 1 1 0 3 3 3 3                                   12     .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .28  0 2 0 0 3 0 3 1 0 0 0 1 1 3 3 3                                               0 3 0 0 3 0 0 0 0 1 3 0 1 3 3 3                                          1.12 1 3 2 2 3 0 3 3 1 3 2 2 3 3 3 3                                               1 3 1 2 3 0 2 3 0 3 2 2 3 3 3 3                                          5.6  3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3                                               3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3                                   63     5.6  3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3                                               3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3                                          1.12 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                               3 3 3 3 3 0 1 2 3 3 3 3 3 3 3 3                                          .28  0 3 2 2 3 0 2 1 1 3 2 1 3 3 3 3                                               1 3 1 1 2 0 0 1 0 3 2 2 2 3 3 3                                          .056 0 1 0 1 0 0 0 0 0 1 1 1 1 1 3 2                                               0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 1                                   57     5.6  1 3 3 3 3 1 3 3 2 3 2 2 3 3 3 3                                               1 3 3 3 3 0 2 2 1 3 2 1 3 3 3 3                                          1.12 0 3 0 0 0 0 2 0 1 1 1 0 1 1 3 3                                               0 2 0 0 0 0 0 0 0 1 0 0 1 0 3 3                                          .28  0 3 0 0 0 0 0 0 0 0 0 0 0 0 2 1                                          .056 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   13     .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .28  0 2 0 1 3 0 1 0 1 0 0 0 3 3 3 3                                               0 0 0 0 3 0 0 0 0 0 0 0 3 3 3 3                                          1.12 1 3 2 2 3 0 3 3 2 2 3 0 2 3 3 3                                               1 3 1 1 2 0 2 2 2 3 3 1 1 3 3 3                                          5.6  3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3                                               3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                   96     .28  0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                          1.12 0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                          5.6  0 1 0 0 0 0 0 0 1 0 --                                                                              0 0 1 3 2                                   8      5.6  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   46     5.6  2 3 1 3 3 1 3 2 1 3 1 0 3 3 3 3                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 2                                   61     5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                               3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .28  0 1 0 1 2 0 1 0 1 1 1 0 2 2 3 3                                               0 1 0 0 2 0 0 0 0 2 0 0 2 3 3 3                                          1.12 1 2 0 2 3 0 2 2 2 3 3 0 3 3 3 3                                               0 3 0 2 3 0 1 2 2 3 2 1 3 3 3 3                                   92     5.6  1 3 3 3 3 1 1 1 2 3 --                                                                              1 3 3 3 3                                          1.12 1 1 0 0 0 0 0 0 0 2 --                                                                              0 0 0 1 0                                          .056 0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                          .28  0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                   89     5.6  0 0 0 0 0 0 0 0 0 1 --                                                                              0 0 0 1 1                                          1.12 0 0 0 0 0 0 0 0 0 1 --                                                                              0 0 0 1 2                                   40     .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .28  0 0 0 0 0 --                                                                              0 0 0 0 0 0 0 0 0 0                                          1.12 0 1 2 1 3 0 1 0 0 2 1 2 1 3 3 3                                          5.6  2 3 3 3 3 1 2 3 2 3 3 2 3 3 3 3                                   59     1.12 3 3 3 3 3 0 3 3 2 3 --                                                                              2 3 3 3 3                                               3 3 3 3 3 0 0 3 2 3 --                                                                              3 3 3 3 3                                          .28  0 2 0 2 2 0 0 0 0 0 --                                                                              0 3 3 3 3                                          5.6  3 3 3 3 3 1 3 3 3 3 --                                                                              3 3 3 3 3                                               3 3 3 3 3 1 3 3 3 3 --                                                                              3 3 3 3 3                                          .056 0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                   60     5.6  0 1 3 0 0 0 0 0 1 1 --                                                                              0 1 3 3 3                                          1.12 0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                          .28  0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                   52     .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .056 0 3 1 1 2 0 1 1 0 3 1 1 2 3 3 3                                               0 3 0 0 2 0 0 0 0 3 3 1 2 3 3 3                                          .28  2 3 3 3 3 0 3 2 3 3 3 2 3 3 3 3                                               1 3 3 3 3 0 1 2 3 3 3 2 3 3 3 3                                          1.12 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                               3 3 3 3 3 0 3 2 3 3 3 2 3 3 3 3                                          5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                               3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          .056 0 2 1 2 1 0 1 2 1 2 2 1 2 3 2 2                                          5.6  3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 3                                          1.12 2 3 3 3 3 2 3 3 2 3 3 2 3 3 3 3                                          .28  1 3 3 3 3 1 3 3 2 3 2 2 3 3 3 3                                   62     .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2                                          1.12 0 0 0 0 0 0 0 0 0 3 1 0 0 0 3 3                                          5.6  1 3 2 2 3 1 3 2 3 3 3 2 0 3 3 3                                   90     .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2                                          5.6  0 0 0 0 1 0 0 0 0 2 0 1 1 2 3 3                                   18     .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 1 2 1 2 3 0 0 2 2 3 2 0 3 3 3 3                                          5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   29     5.6  0 2 2 1 3 0 1 0 1 2 1 0 1 3 3 3                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   47     5.6  1 3 3 3 3 0 2 2 2 3 3 2 3 3 3 3                                          1.12 0 1 0 0 0 0 1 0 0 0 0 1 0 1 1 0                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   93     .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          5.6  1 3 3 3 3 2 1 3 2 3 3 2 3 3 3 3                                          1.12 0 1 0 0 0 0 0 0 0 1 1 1 0 2 1 2                                          .056 0 1 0 0 0 0 0 0 0 1 1 0 0 0 0 1                                   15     5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 0 3 2 3 3 0 2 2 2 3 3 2 3 3 3 3                                          .28  0 1 0 0 0 0 0 0 1 1 1 0 0 1 3 3                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   44     .056 0 0 0 0 0 0 0 0 0 2 1 0 0 0 0 1                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1                                          1.12 0 1 0 1 3 0 1 0 2 2 2 0 1 3 3 3                                          5.6  1 3 3 3 3 0 2 2 3 3 3 2 3 3 3 3                                   31     5.6  0 2 0 1 3 0 2 2 2 3 1 0 3 3 3 3                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1                                          1.12 0 2 0 0 0 0 0 0 0 2 0 0 2 1 2 1                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   53     1.12 3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3                                               3 3 3 3 3 0 2 3 3 3 3 3 3 3 3 3                                          5.6  3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3                                               3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3                                          .28  0 3 3 3 3 0 2 2 3 3 3 2 3 3 3 3                                               0 3 3 3 3 0 0 1 1 3 2 2 3 3 3 3                                          .056 2 3 3 3 1 0 1 3 3 3 3 2 0 3 3 3                                               1 3 2 3 0 0 0 2 2 3 3 1 0 3 3 3                                          .0112                                                                              0 3 0 2 1 0 2 1 2 3 2 2 0 2 2 3                                               0 2 0 1 0 0 0 0 0 0 0 0 0 1 2 3                                   16     5.6  3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3                                          1.12 2 3 3 3 3 2 3 3 3 3 3 2 3 3 3 3                                          .28  0 1 0 2 2 0 1 2 2 2 2 1 3 3 3 3                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 3                                          .0112                                                                              0 0 0 0 0 0 0 1 0 1 0 0 0 0 1 0                                   21     5.6  0 2 1 1 1 0 0 1 2 3 3 2 3 3 3 3                                          1.12 0 0 0 0 0 0 0 0 0 2 2 0 0 0 2 2                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   64     .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1                                          5.6  2 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 1 3 0 2 3 0 3 3 3 3 3 2 3 3 3 3                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 2 2 2                                   54     .0112                                                                              0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 1 1                                          5.6  3 3 3 3 3 3 3 3 3 3 --                                                                              3 3 3 3 3                                          .056 2 2 0 2 2 0 0 0 1 2 --                                                                              0 3 3 3 3                                          1.12 3 3 3 3 3 0 3 3 3 3 --                                                                              3 3 3 3 3                                          .28  2 3 3 3 3 0 3 3 2 3 --                                                                              2 3 3 3 3                                   11     5.6  2 3 3 3 3 0 3 3 3 3 --                                                                              3 3 3 3 3                                          1.12 1 3 1 3 3 0 3 3 3 3 --                                                                              3 3 3 3 3                                          .28  0 2 0 3 1 0 1 0 1 1 --                                                                              1 0 2 2 3                                          .056 0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 1 0                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                   87     5.6  3 3 3 3 3 0 3 3 3 3 --                                                                              3 3 3 3 3                                          1.12 2 3 2 3 3 0 3 3 2 3 --                                                                              2 3 3 3 3                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 1 0                                          .28  1 2 0 0 3 0 1 0 0 0 --                                                                              1 1 3 3 3                                   97     5.6  1 3 0 0 0 0 0 0 2 2 1 0 0 3 3 3                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 0 0 0 0 0 0 0 0 1 1 0 0 0 1 1 1                                   20     5.6  1 3 3 1 3 0 2 3 2 3 --                                                                              2 3 3 3 3                                          1.12 0 0 0 0 0 0 0 0 0 1 --                                                                              1 0 0 1 2                                          .28  0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                   22     5.6  0 2 1 1 3 1 3 2 2 3 --                                                                              2 3 3 3 3                                          1.12 0 0 0 0 0 0 0 0 0 0 --                                                                              0 1 2 2 2                                          .28  0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                   75     .28  0 2 1 2 1 0 3 2 1 2 --                                                                              1 3 1 3 3                                          .056 1 2 0 2 0 0 0 0 0 0 --                                                                              0 0 0 2 2                                          5.6  0 3 3 3 3 1 3 3 3 3 --                                                                              1 3 3 3 3                                          1.12 0 2 2 2 3 0 2 1 1 3 --                                                                              1 3 2 3 3                                   14     .0112                                                                              0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 2                                          1.12 3 3 3 3 3 1 3 3 3 3 --                                                                              3 3 3 3 3                                          5.6  3 3 3 3 3 2 3 3 3 3 --                                                                              3 3 3 3 3                                          .056 0 2 2 2 3 0 3 1 1 2 --                                                                              1 3 3 3 3                                          .28  2 3 3 3 3 1 3 3 3 3 --                                                                              3 3 3 3 3                                   23     5.6  1 2 0 0 1 0 1 2 0 3 --                                                                              1 2 1 2 3                                          1.12 0 0 0 0 0 0 0 0 0 0 --                                                                              0 1 0 0 1                                          .28  0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                   35     5.6  0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                          1.12 0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                   17     5.6  3 3 3 3 3 3 3 3 3 3 --                                                                              3 3 3 3 3                                          1.12 3 3 3 3 3 2 3 3 3 3 --                                                                              3 3 3 3 3                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 --                                                                              0 2 2 2 3                                          .28  0 1 0 0 2 0 0 2 0 0 --                                                                              0 2 3 3 3                                   34     5.6  0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 2                                          1.12 0 0 0 0 0 0 0 0 0 0 --                                                                              0 1 0 1 0                                   50     5.6  0 2 0 2 3 0 3 2 2 3 --                                                                              0 2 3 3 3                                          1.12 0 1 0 0 0 0 0 1 0 1 --                                                                              0 0 0 1 1                                          .28  0 0 0 0 0 0 0 0 0 --                                                                              --                                                                              0 0 0 0 1                                   55     5.6  3 3 3 3 3 1 3 3 3 3 --                                                                              3 3 3 3 3                                          1.12 3 3 3 3 3 0 3 3 3 3 --                                                                              3 3 3 3 3                                          .28  2 3 2 3 3 0 3 3 3 3 --                                                                              2 3 3 3 3                                          .056 0 2 0 1 3 0 2 2 2 3 --                                                                              2 3 3 3 3                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 2                                   65     .28  0 0 0 0 1 0 0 0 0 0 --                                                                              0 2 2 2 2                                          .056 0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 1 2 1                                          5.6  1 3 3 3 3 0 3 3 3 3 --                                                                              2 3 3 3 3                                          1.12 0 1 3 2 3 0 3 0 1 2 --                                                                              0 3 3 3 3                                   68     .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          5.6  0 0 0 0 1 0 0 2 0 0 0 0 3 1 1 3                                   67     5.6  3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3                                          1.12 3 3 3 3 3 2 3 3 3 3 3 2 3 3 3 3                                          .28  1 3 3 3 3 0 3 2 2 3 3 1 3 3 3 3                                          .056 0 0 0 0 3 0 2 1 0 1 0 0 1 1 1 2                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 2                                   82     5.6  0 0 0 0 3 0 0 1 0 1 1 1 1 1 2 3                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   84     5.6  1 3 3 3 3 1 3 3 3 3 3 2 3 3 3 3                                          1.12 0 2 0 2 3 0 2 2 1 0 0 0 3 3 3 3                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   85     5.6  3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3                                          1.12 1 3 3 3 3 0 2 2 2 3 3 2 3 3 3 3                                          .28  0 2 0 1 1 0 1 2 0 2 1 0 2 2 2 2                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 2                                   86     .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 2 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          .28  1 2 3 3 3 0 3 1 2 2 2 1 3 3 3 3                                          .056 0 2 0 1 3 0 2 0 1 2 1 0 2 2 2 3                                   112    .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1                                          1.12 0 2 1 0 3 0 2 1 1 1 1 2 2 2 2 2                                          5.6  0 3 3 2 3 3 3 3 3 3 3 2 3 3 3 3                                   70     5.6  0 2 2 2 2 0 2 2 3 3 --                                                                              1 3 3 3 3                                          .28  0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                          1.12 0 1 0 0 0 0 0 0 0 0 --                                                                              0 0 1 2 3                                          .056 0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                   24     1.12 0 3 3 2 2 0 2 2 2 3 2 2 3 3 3 3                                          5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          2.8  0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 2                                   71     5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 1 2 3 2 3 0 2 2 2 3 3 2 2 3 3 3                                          .28  0 1 0 0 1 0 0 0 0 0 0 0 0 2 2 2                                   103    .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          5.6  1 2 3 2 3 0 3 3 1 3 2 1 3 3 3 3                                   69     1.12 3 3 3 3 3 0 3 3 3 3 --                                                                              3 3 3 3 3                                          .28  0 3 3 3 3 0 3 3 2 3 --                                                                              1 3 3 3 3                                          .056 0 0 0 0 2 0 3 1 0 0 --                                                                              1 2 3 3 3                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 1 1 2                                          5.6  3 3 3 3 3 2 3 3 3 3 --                                                                              3 3 3 3 3                                   72     5.6  3 3 3 3 3 0 3 3 3 3 --                                                                              3 3 3 3 3                                          1.12 2 3 3 3 3 0 3 3 3 3 --                                                                              2 3 3 3 3                                          .28  0 1 3 2 3 0 3 3 2 3 --                                                                              1 1 3 3 3                                          .056 0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 1 2                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                   99     5.6  0 0 0 0 0 0 0 0 0 1 1 0 0 0 0 1                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   81     5.6  2 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3                                          1.12 0 3 0 1 3 0 2 1 1 3 3 1 1 3 3 3                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   42     1.12 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          5.6  1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   74     .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1                                          1.12 0 3 0 1 3 --                                                                              0 2 1 2 2 0 1 3 3 3                                          5.6  1 3 3 3 3 0 3 3 2 3 3 2 3 3 3 3                                   73     5.6  2 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3                                          1.12 2 3 2 2 3 0 3 1 2 3 3 2 3 3 3 3                                          .28  0 1 1 1 2 0 0 0 0 1 0 0 0 0 2 3                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2                                   10     .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 0 2 0 1 1 0 2 1 0 1 1 0 1 2 2 3                                          5.6  1 3 3 3 3 0 3 3 3 3 3 1 3 3 3 3                                   101    .056 0 2 0 0 3 0 2 0 1 3 2 0 2 3 3 3                                          .28  0 3 2 0 3 0 3 2 3 3 3 3 3 3 3 3                                          1.12 1 3 3 1 3 3 3 3 3 3 3 3 3 3 3 3                                          5.6  3 3 3 2 3 3 3 3 3 3 3 3 3 3 3 3                                          .056 0 1 0 0 3 1 2 2 2 3 2 1 2 3 3 3                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 2                                          .28  1 3 2 0 3 1 3 1 3 3 3 2 3 3 3 3                                          .056 0 2 0 0 3 0 1 0 0 0 0 2 1 2 3 3                                   25     .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          5.6  3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3                                          1.12 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3                                          .28  0 3 3 2 3 0 3 1 2 3 3 3 3 3 3 3                                          .056 0 2 1 0 1 0 0 0 0 0 0 0 1 2 3 3                                   102    5.6  1 2 0 0 0 0 0 0 0 2 2 1 1 1 1 3                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   134    5.6  3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3                                          1.12 1 2 2 2 3 2 2 2 2 2 2 1 3 3 3 3                                          .28  1 0 0 0 1 0 0 0 0 0 0 0 0 0 0 2                                          .0112                                                                              0 0 0 0 0 --                                                                              0 0 0 0 0 0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   130    5.6  0 0 0 3 3 0 2 1 1 3 2 0 0 1 1 3                                          1.12 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 2                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1                                   104    .28  0 0 0 0 2 0 0 0 0 1 0 0 0 0 0 1                                          5.6  1 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3                                          1.12 0 2 0 1 3 0 2 2 1 2 1 1 2 2 2 2                                   127    .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 0 1 0 0 0 0 0 0 0 0 0 0 0 1 2 1                                          5.6  0 3 1 1 3 0 1 2 2 3 2 3 2 3 3 3                                   129    5.6  2 3 2 3 3 0 3 3 3 3 3 3 3 3 3 3                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 0 2 0 2 3 --                                                                              0 0 2 3 3 3 1 3 3 3                                          .28  0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 1                                   131    .056 0 0 0 0 3 0 0 0 0 2 2 1 0 3 3 3                                          5.6  3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3                                          1.12 2 3 3 0 3 --                                                                              3 3 3 3 3 3 3 3 3 3                                          .28  0 3 1 0 3 0 3 3 3 3 3 3 3 3 3 3                                          .0112                                                                              0 0 0 0 0 --                                                                              0 0 0 0 0 0 0 0 0 0                                   133    5.6  3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3                                          1.12 2 3 3 2 3 0 3 3 3 3 3 3 3 3 3 3                                          .28  2 3 0 0 3 1 3 3 3 3 3 3 3 3 3 3                                          .056 0 2 0 0 3 0 2 1 1 1 1 2 1 3 3 3                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 2                                   80     .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2                                          5.6  3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3                                          .056 0 1 0 0 2 0 0 0 0 2 1 0 0 1 1 3                                          .28  1 3 3 3 3 3 3 3 3 3 3 2 3 3 3 3                                          1.12 2 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3                                   26     5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 1 2 2 2 3 0 3 2 1 1 0 1 3 3 3 3                                          .28  0 2 0 0 0 0 0 0 0 0 0 0 2 2 3 1                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   27     5.6  2 3 3 3 3 0 3 1 2 3 2 1 3 3 3 3                                          1.12 1 0 0 0 3 0 1 0 0 1 0 1 2 1 2 3                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   123    .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .0112                                                                              0 0 0 0 0 --                                                                              0 0 0 0 0 0 0 0 0 0                                          1.12 0 3 3 3 3 0 3 1 2 3 3 3 3 3 3 3                                          .28  0 2 1 0 3 0 2 0 1 2 1 1 3 3 3 3                                          5.6  3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3                                   124    .28  0 0 0 0 0 0 0 0 0 0 0 0 0 2 3 3                                          .056 0 0 0 0 0 --                                                                              0 0 0 0 0 0 0 0 0 1                                          1.12 0 1 3 2 3 0 2 2 2 2 1 1 3 3 3 3                                          5.6  1 2 3 3 3 0 3 2 2 3 3 3 3 3 3 3                                   109    1.12 0 0 0 0 0 0 3 0 0 0 0 0 0 0 0 0                                          5.6  0 0 0 0 0 --                                                                              1 0 0 0 0 0 1 2 2 3                                   110    .28  0 1 0 0 2 0 1 0 0 1 0 0 3 2 1 1                                          1.12 0 3 2 3 3 0 3 0 1 3 2 0 3 3 3 3                                          5.6  0 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   111    1.12 1 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          .28  1 2 3 3 3 0 2 0 1 1 1 1 3 3 3 3                                          5.6  3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3                                          .056 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2                                          .0112                                                                              0 0 0 0 0 --                                                                              0 0 0 0 0 0 0 0 0 0                                   122    5.6  3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 1 3 2 2 3 0 3 2 2 3 3 3 3 3 3 3                                          .28  0 2 0 0 2 0 1 0 0 1 1 1 2 2 2 3                                          .056 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0                                   117    .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          5.6  3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3                                          1.12 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          .28  1 3 2 3 3 0 3 2 3 3 3 2 3 3 3 3                                          .056 0 2 0 0 3 0 3 0 1 1 1 0 3 3 3 3                                   113    .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .28  0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 2                                          1.12 0 3 2 0 3 0 3 1 2 3 3 2 3 3 3 3                                          5.6  0 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                   125    .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .0112                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 0 2 2 3 3 2 3 3 3 3 3 2 3 3 3 3                                          .28  0 2 0 0 3 0 2 0 1 2 2 1 3 3 3 3                                   152    5.6  1 2 0 2 3 0 0 0 1 2 2 0 3 3 3 3                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 N 2 3 3                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 N 0 0 0                                   153    5.6  0 2 1 0 1 0 1 1 1 2 2 1 1 2 3 3                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   156    5.6  1 2 0 0 0 0 0 1 1 2 2 0 0 0 1 3                                          1.12 1 1 0 0 0 0 0 0 2 2 2 0 0 0 1 2                                   157    5.6  0 2 0 0 0 0 0 0 0 3 3 0 0 2 3 3                                          1.12 0 3 0 N 0 0 0 1 2 3 3 0 0 2 3 3                                          0.28 0 2 0 0 0 0 0 0 0 3 2 0 0 0 1 2                                   158    5.6  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   159    5.6  0 2 3 3 3 0 3 2 2 3 3 3 3 3 3 3                                          1.12 0 2 0 1 3 0 2 1 0 0 0 0 2 3 3 3                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2                                   161    5.6  0 3 3 2 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 1 3 0 1 3 0 2 2 2 3 3 2 3 3 3 3                                          0.28 0 0 0 0 0 0 0 0 1 1 1 1 1 1 2 3                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   162    5.6  1 3 3 3 3 0 2 3 3 3 3 3 3 3 3 3                                          1.12 0 2 0 2 2 1 2 2 1 2 2 1 2 3 3 3                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   163    5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 0 2 3 1 3 0 2 1 2 3 3 3 3 3 3 3                                          0.28 0 0 2 0 1 0 0 0 0 1 1 1 0 1 1 2                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1                                          0.0112                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   164    5.6  0 3 1 0 3 1 3 2 2 2 2 2 3 2 3 3                                          1.12 1 2 0 0 0 0 0 0 0 2 2 2 1 2 0 0                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   165    5.6  0 0 0 0 2 0 0 1 0 0 0 1 0 3 3 3                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 2 1 2                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   166    5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          0.28 0 2 2 2 3 0 3 2 2 3 3 2 3 3 3 3                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 2 3 3                                          0.0112                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   167    5.6  0 2 2 3 3 0 2 3 3 3 3 2 3 3 3 3                                          1.12 0 0 0 1 1 0 2 1 2 2 1 1 N 1 1 2                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 N 0 0 0                                   169    5.6  0 3 3 3 3 0 1 2 3 3 3 3 3 3 3 3                                          1.12 0 2 0 0 3 0 2 1 0 2 2 0 3 3 3 3                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          0.0112                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   170    5.6  2 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 0 3 3 2 2 0 2 0 1 3 3 3 3 2 3 3                                          0.28 0 0 0 0 2 0 0 0 0 2 1 1 1 2 2 3                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2                                          0.0112                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   171    5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 0 3 3 2 3 0 3 3 3 3 3 3 3 3 3 3                                          0.28 0 2 0 0 3 0 0 1 0 0 0 0 3 3 3 3                                          .056 0 1 0 0 1 0 0 0 0 0 0 0 0 1 2 0                                          0.0112                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   172    5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          0.28 0 3 3 3 3 0 1 2 1 3 3 2 3 3 3 3                                          .056 0 1 1 0 3 0 0 0 0 0 0 0 0 3 3 3                                          0.0112                                                                             0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 0                                   173    5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 2 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          0.28 0 2 1 0 3 0 2 0 0 1 1 0 3 3 3 3                                          .056 0 1 0 0 0 0 0 0 0 0 0 0 0 1 3 3                                          0.0112                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   174    5.6  1 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 0 0 0 0 3 0 0 0 0 0 0 0 1 2 3 3                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   175    5.6  0 3 2 1 3 0 3 3 1 3 2 2 3 3 3 3                                          1.12 0 2 0 0 1 0 2 0 0 2 0 0 3 2 3 3                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   176    5.6  0 3 3 0 3 0 3 3 1 3 3 2 3 3 3 3                                          1.12 0 1 0 0 3 0 0 0 0 0 0 0 0 3 3 1                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   177    5.6  1 3 3 3 3 0 3 3 3 3 3 2 3 3 3 3                                          1.12 0 1 1 1 0 0 0 0 0 2 1 1 2 2 2 2                                          0.28 0 1 0 0 0 0 0 0 0 2 1 0 0 0 1 1                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          0.0112                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   178    5.6  3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3                                          1.12 1 3 3 2 3 0 3 2 2 3 2 2 3 3 3 3                                          0.28 0 2 1 1 3 0 1 0 1 1 0 0 1 2 3 3                                          0.56 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   179    5.6  0 3 3 2 3 0 3 1 2 3 3 2 3 3 3 3                                          1.12 0 0 0 0 2 0 3 0 0 0 0 0 3 3 3 3                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   180    5.6  2 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 0 3 1 2 3 0 3 0 2 2 2 1 3 3 3 3                                          0.28 0 1 0 0 2 0 0 0 1 2 0 1 2 1 3 3                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   181    5.6  0 0 0 0 1 0 0 0 0 0 0 0 0 0 3 2                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   182    5.6  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   184    5.6  1 3 3 1 3 1 3 2 2 3 3 3 3 3 3 3                                          1.12 0 0 1 0 0 0 0 0 0 2 2 1 0 1 2 3                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   186    5.6  1 3 3 2 3 1 2 2 2 3 3 3 3 3 3 3                                          1.12 0 2 0 0 0 0 0 0 0 2 1 1 0 2 2 3                                          0.28 0 1 0 0 0 N 1 0 0 0 0 2 2 1 2 2                                          .056 0 0 0 0 0 0 0 0 0 1 1 0 0 0 0 0                                   187    5.6  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   189    5.6  1 2 3 1 3 0 3 1 2 3 3 2 3 3 3 3                                          1.12 0 0 0 0 0 0 0 0 0 1 0 0 0 1 2 3                                   190    5.6  3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3                                          1.12 2 2 3 1 3 0 2 2 2 3 2 1 3 3 3 3                                          0.28 2 3 3 1 1 0 2 2 2 2 2 1 1 3 3 3                                          .056 0 1 0 0 0 0 0 0 0 2 2 1 1 1 0 2                                          0.0112                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   191    5.6  0 2 1 1 2 0 1 0 2 3 3 2 2 3 3 3                                          1.12 1 1 0 0 0 N 0 1 2 2 2 N 1 1 2 3                                          0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   192    5.6  0 1 0 0 0 N 0 0 0 0 0 0 0 1 3 3                                          1.12 0 0 0 0 0 N 0 0 0 0 0 0 0 0 0 0                                   198    5.6  3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3                                          1.12 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          0.28 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          .056 1 2 2 3 3 0 3 3 3 3 2 2 3 3 3 3                                          .056 0 3 2 3 3 N 3 2 2 3 3 2 3 3 3 3                                          0.0112                                                                             0 0 0 0 1 0 0 0 1 2 1 2 1 2 2 3                                          0.0112                                                                             0 0 0 0 1 N 1 0 0 0 0 1 0 0 1 2                                          .0056                                                                              0 0 0 0 0 N 0 0 0 1 1 1 0 0 1 2                                   199    5.6  3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3                                          1.12 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          0.28 2 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          .056 1 2 1 2 3 0 2 1 2 3 2 1 3 3 3 3                                          .056 0 3 1 2 3 N 2 2 3 3 3 1 3 3 3 3                                          0.0112                                                                             0 0 1 1 3 0 1 0 0 0 0 1 3 3 3 3                                          0.0112                                                                             0 0 0 0 2 N 2 0 0 0 0 0 1 0 2 2                                          .0056                                                                              0 0 0 0 0 N 0 0 0 0 0 0 0 0 1 1                                   200    5.6  2 3 2 1 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 0 2 0 0 0 N 3 1 2 3 3 1 1 2 3 3                                          0.28 0 2 0 0 0 0 1 0 0 1 1 0 1 2 2 3                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   204    5.6  0 0 0 0 0 0 0 0 0 0 0 0 3 3 3 3                                          1.12 0 0 0 0 0 0 0 0 0 0 0 0 N 0 0 2                                   208    5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 1 3 3 3 3 0 3 3 2 3 3 3 3 3 3 3                                          0.28 0 1 0 1 3 0 0 0 0 1 1 1 3 3 3 3                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 N 1 2 3                                          0.0112                                                                             0 0 0 0 0 0 0 0 0 0 0 0 N 0 0 0                                   209    5.6  3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3                                          1.12 0 3 3 3 3 0 3 3 3 3 3 2 3 3 3 3                                          0.28 0 1 0 1 3 0 0 0 0 0 0 0 3 3 3 3                                          .056 0 0 0 0 0 0 0 0 0 0 0 0 N 1 1 2                                          0.0112                                                                             0 0 0 0 0 0 0 0 0 0 0 0 N 0 0 0                                   __________________________________________________________________________

The post-emergence herbicidal activity of some of the various compoundsof this invention was demonstrated by greenhouse testing in thefollowing manner. A good grade of top soil is placed in aluminum panshaving holes in the bottom and compacted to a depth of 0.95 to 1.27 cm.from the top of the pan. A predetermined number of seeds of each ofseveral dicotyledonous and monocotyledonous annual plant species and/orvegetative propagules for the perennial plant species were placed on thesoil and pressed into the soil surface. The seeds and/or vegetativepropagules are covered with soil and leveled. The pans are then placedon a sand bench in the greenhouse and watered from below as needed.After the plants reach the desired age (two to three weeks), each pan,except for the control pans, is removed individually to a sprayingchamber and sprayed by means of an atomizer at the rate noted. In thespray solution is an amount of an emulsifying agent mixture to give aspray solution or suspension which contains about 0.4% by weight of theemulsifier. The spray solution or suspension contains a sufficientamount of the candidate chemical in order to give application ratescorresponding to those set forth in the tables. The pans were returnedto the greenhouse and watered as before and the injury to the plants ascompared to the control is observed at approximately 10-14 days (usually11 days) and in some instances observed again at 24-28 days (usually 25days) after spraying.

The post-emergent herbicidal activity index used in Table II is asfollows:

    ______________________________________                                        Plant Response    Index                                                       ______________________________________                                        0-24%        Inhibition                                                                             0                                                       25-49%       Inhibition                                                                             1                                                       50-74%       Inhibition                                                                             2                                                       75-99%       Inhibition                                                                             3                                                       100%         Inhibition                                                                             4                                                       ______________________________________                                    

The letter identifying plants used in the following tests are identicalto those used for corresponding tests in the pre-emergence tests inTable I above.

                                      TABLE 23                                    __________________________________________________________________________    Example                                                                       No.  kg/ha                                                                             A  B C   D E   F G   H I   J K                                       __________________________________________________________________________     6   11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        7   11.2                                                                              -- 0 0   0 0   0 0   0 0   0 0                                        94  11.2                                                                              -- 0 0   0 0   0 0   0 0   0 0                                        95  11.2                                                                              -- 0 0   0 0   0 0   0 0   0 1                                        12  11.2                                                                              0  0 1   1 0   0 0   0 0   0 2                                        38  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        32  11.2                                                                              2  0 0   0 0   0 0   0 0   0 0                                        37  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                        13  11.2                                                                              0  1 0   2 0   0 0   0 0   0 2                                        39  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        28  11.2                                                                              0  1 0   0 0   0 0   0 0   0 0                                        96  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        19  11.2                                                                              -- 0 0   0 0   0 0   0 0   0 0                                        8   11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        46  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        61  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        45  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        88  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        92  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        89  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        27  11.2                                                                              3  0 0   0 0   --                                                                              0   0 0   0 0                                        59  11.2                                                                              -- 0 0   0 0   --                                                                              0   0 0   0 0                                        60  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        91  11.2                                                                              -- 0 0   0 0   --                                                                              0   0 0   0 0                                        52  11.2                                                                              -- 0 0   0 0   --                                                                              0   0 0   0 0                                        58  11.2                                                                              -- 0 0   0 0   --                                                                              0   0 0   0 0                                        62  11.2                                                                              -- 0 1   0 0   --                                                                              0   0 0   0 0                                        90  11.2                                                                              -- 0 0   0 0   --                                                                              0   0 0   0 0                                        18  11.2                                                                              -- 0 0   0 0   --                                                                              0   0 0   0 0                                        40  11.2                                                                              -- 1 0   0 0   0 0   0 0   0 0                                        29  11.2                                                                              -- 1 0   1 0   0 0   0 0   0 0                                        47  11.2                                                                              -- 1 0   1 0   --                                                                              0   0 0   0 0                                        48  11.2                                                                              -- 0 0   0 0   0 0   0 0   0 0                                        46  11.2                                                                              -- 0 0   0 0   0 0   0 0   0 0                                        15  11.2                                                                              0  1 1   1 0   0 0   0 0   0 0                                        44  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                        31  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        53  11.2                                                                              0  1 0   1 0   0 0   0 0   0 1                                        16  11.2                                                                              0  1 1   1 1   0 0   0 0   0 1                                        21  11.2                                                                              0  1 1   2 0   0 0   0 0   0 0                                        64  11.2                                                                              0  1 1   2 0   0 0   0 0   0 0                                        32  11.2                                                                              0  0 0   1 1   0 0   0 0   0 0                                        54  11.2                                                                              0  1 1   2 0   1 0   0 0   0 2                                        37  11.2                                                                              0  1 0   0 0   0 0   0 0   0 0                                        11  11.2                                                                              0  0 0   1 0   --                                                                              0   0 0   0 0                                        87  11.2                                                                              0  1 0   1 0   --                                                                              0   0 0   0 0                                        97  11.2                                                                              0  0 0   0 --  0 0   0 0   0 0                                        20  11.2                                                                              -- 1 0   1 0   --                                                                              0   0 0   0 0                                        41  11.2                                                                              -- 0 0   0 0   --                                                                              0   0 0   0 0                                        22  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        75  11.2                                                                              0  0 1   0 0   --                                                                              0   0 0   0 0                                        14  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        30  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        23  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        35  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        17  11.2                                                                              0  --                                                                              1   2 0   0 0   0 1   0 2                                        34  11.2                                                                              0  0 0   0 0   0 0   0 --  0 0                                        50  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        55  11.2                                                                              0  2 1   2 2   --                                                                              2   0 0   1 2                                        55* 11.2                                                                              0  2 2   2 3   --                                                                              2   1 0   2 2                                        33  11.2                                                                              0  1 0   1 1   --                                                                              0   0 0   0 0                                        49  11.2                                                                              0  0 0   1 0   --                                                                              0   0 0   0 0                                        65  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        51  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        68  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        67  11.2                                                                              0  0 0   0 0   0 0   0 0   0 1                                        76  11.2                                                                              0  1 0   1 2   0 1   0 1   0 1                                        77  11.2                                                                              0  1 1   1 1   1 0   0 0   0 0                                        83  11.2                                                                              0  0 1   0 0   0 0   0 0   0 0                                        82  11.2                                                                              0  0 1   1 0   0 0   0 0   0 0                                        84  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        66  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        85  11.2                                                                              1  0 0   0 0   0 2   0 0   0 2                                        86  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       112  11.2                                                                              2  --                                                                              1   1 0   0 0   0 0   0 0                                        70  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        24  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        36  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        71  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       103  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       100  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                        69  11.2                                                                              0  1 0   0 0   --                                                                              0   0 0   0 1                                        72  11.2                                                                              0  0 0   0 0   --                                                                              0   0 0   0 0                                        99  11.2                                                                              0  --                                                                              0   0 0   0 0   0 0   0 0                                        81  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                        42  11.2                                                                              -- 0 0   0 0   0 0   0 0   0 0                                        74  11.2                                                                              0  1 0   1 0   0 0   0 0   0 1                                        78  11.2                                                                              -- 0 0   0 0   0 0   0 0   0 1                                        73  11.2                                                                              0  1 1   1 0   0 0   0 0   0 0                                        98  11.2                                                                              0  0 0   0 0   0 0   --                                                                              0   0 0                                        10  11.2                                                                              0  --                                                                              0   0 0   0 0   0 0   0 0                                       101  11.2                                                                              -- 0 0   0 0   1 0   0 0   0 2                                        25  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                       102  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       134  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       130  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       128  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       104  11.2                                                                              0  0 0   0 2   0 0   0 0   0 0                                       127  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                       129  11.2                                                                              0  1 1   2 3   0 0   0 0   0 0                                       131  11.2                                                                              0  1 0   1 0   0 0   0 0   0 2                                       105  11.2                                                                              0  0 1   1 0   0 0   0 0   0 1                                       133  11.2                                                                              0  1 1   1 1   1 0   0 0   0 2                                        80  11.2                                                                              0  1 1   1 1   0 0   0 0   0 1                                        79  11.2                                                                              -- 0 0   0 0   0 0   0 0   0 0                                        26  11.2                                                                              -- 0 0   0 0   0 0   0 0   0 0                                        27  11.2                                                                              -- 0 0   0 0   0 0   0 0   0 0                                       123  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                       124  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                       119  11.2                                                                              0  1 0   0 0   0 0   0 0   0 0                                       109  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                        43  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       107  11.2                                                                              0  --                                                                              0   0 0   0 0   0 0   0 0                                       110  11.2                                                                              0  0 0   1 0   0 0   0 0   0 1                                       111  11.2                                                                              0  --                                                                              1   2 0   0 0   0 0   0 1                                       106  11.2                                                                              0  --                                                                              0   0 0   0 0   0 0   0 0                                       120  11.2                                                                              0  --                                                                              0   1 0   0 0   0 0   0 0                                       122  11.2                                                                              0  1 1   1 0   0 0   0 0   0 0                                       117  11.2                                                                              0  1 1   2 1   0 0   0 0   0 0                                       118  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       113  11.2                                                                              0  1 1   2 0   0 0   0 0   0 0                                       121  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                       125  11.2                                                                              1  1 0   1 1   0 0   0 0   0 1                                       137  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       136  11.2                                                                              0  1 1   2 1   0 0   0 0   0 0                                       135  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       138  11.2                                                                              0  0 1   1 0   0 1   0 1   1 2                                       138  11.2                                                                              0  1 1   1 0   0 0   0 0   0 1                                       139  11.2                                                                              0  1 0   1 0   0 0   0 0   0 0                                       140  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       141  11.2                                                                              0  0 1   1 0   1 0   0 N   0 0                                       142  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       143  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       144  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       146  11.2                                                                              1  0 2   1 2   1 0   0 N   0 0                                       147  11.2                                                                              0  1 1   1 1   0 0   0 N   0 0                                       148  11.2                                                                              1  1 1   1 2   0 0   0 0   0 1                                       149  11.2                                                                              N  0 1   1 0   0 0   0 0   0 0                                       150  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       152  11.2                                                                              0  0 0   0 1   0 0   0 N   0 0                                       153  11.2                                                                              0  1 0   0 0   0 0   0 0   0 0                                       154  11.2                                                                              0  0 0   0 0   0 0   0 --  0 0                                       155  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       156  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       157  11.2                                                                              0  2 1   2 0   0 0   0 0   0 1                                       158  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       159  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                       160  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       161  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                       162  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                       163  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       164  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       165  11.2                                                                              0  0 0   1 1   0 0   0 0   0 0                                       166  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       167  11.2                                                                              0  1 0   1 0   0 0   0 0   0 0                                       170  11.2                                                                              0  1 1   1 0   0 1   0 0   0 0                                       171  11.2                                                                              1  1 1   1 0   0 0   0 0   0 0                                       172  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                       173  11.2                                                                              0  1 0   1 0   0 0   0 0   0 0                                       174  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       175  11.2                                                                              0  0 1   1 0   0 0   0 0   0 0                                       176  11.2                                                                              0  1 0   0 0   0 0   0 0   0 0                                       177  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       178  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       179  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       180  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       181  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       182  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       183  11.2                                                                              0  0 0   0 2   0 0   0 0   0 0                                       184  11.2                                                                              N  0 0   0 0   0 0   0 0   0 0                                       185  11.2                                                                              N  0 0   0 0   0 0   0 0   0 0                                       186  11.2                                                                              0  1 0   0 0   0 0   0 --  0 0                                       187  11.2                                                                              0  0 0   0 0   0 0   0 --  0 0                                       189  11.2                                                                              0  1 1   0 0   0 0   0 N   0 0                                       190  11.2                                                                              0  0 0   0 0   0 0   0 --  0 0                                       191  11.2                                                                              N  0 1   1 0   0 0   0 --  0 0                                       192  11.2                                                                              0  0 0   0 0   0 0   0 --  0 0                                       193  11.2                                                                              N  0 1   0 0   0 0   0 N   0 0                                       194  11.2                                                                              0  1 0   1 0   0 0   0 N   0 0                                       195  11.2                                                                              0  1 1   1 0   0 0   0 N   0 0                                       196  11.2                                                                              0  1 1   1 0   0 0   0 N   0 0                                       197  11.2                                                                              0  0 0   0 0   0 0   0 N   0 0                                       198  11.2                                                                              0  0 0   1 0   0 0   0 N   0 0                                       199  11.2                                                                              0  0 0   0 0   0 0   0 N   0 0                                       200  11.2                                                                              0  1 0   1 1   0 0   0 --  0 0                                       201  11.2                                                                              1  0 0   0 0   0 0   N N   0 1                                       202  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       203  11.2                                                                              0  0 0   0 0   0 0   0 N   0 0                                       204  11.2                                                                              0  0 0   0 1   0 0   0 N   0 0                                       209  11.2                                                                              0  0 1   0 1   0 0   0 N   0 0                                       210  11.2                                                                              0  0 0   1 0   0 0   0 N   0 0                                       213  11.2                                                                              0  0 0   1 0   0 0   0 N   0 1                                       215  11.2                                                                              N  0 0   1 3   0 0   0 0   0 1                                       216  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       217  11.2                                                                              0  0 0   0 0   0 0   0 N   0 0                                       219  11.2                                                                              N  0 0   0 0   0 0   0 0   0 0                                       220  11.2                                                                              N  0 0   0 0   0 0   0 0   0 0                                       221  11.2                                                                              N  0 0   0 0   0 0   0 0   0 0                                       222  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       223  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       224  11.2                                                                              0  0 0   0 0   0 0   0 0   0 0                                       225  11.2                                                                              N  0 0   0 0   0 0   0 0   0 0                                       226  11.2                                                                              N  0 0   0 0   0 0   0 0   0 0                                       227  11.2                                                                              N  0 1   0 0   0 0   0 0   0 0                                       233  11.2                                                                              N  0 1   0 0   0 0   0 0   0 0                                       234  11.2                                                                              N  0 1   1 0   0 0   0 0   0 0                                       235  11.2                                                                              0  0 1   1 0   0 0   0 0   0 0                                       236  11.2                                                                              0  0 0   1 0   0 0   0 0   0 0                                       237  11.2                                                                              N  0 1   1 0   0 0   0 0   0 0                                       238  11.2                                                                              N  1 1   1 0   1 0   0 0   0 1                                       240  11.2                                                                              2  0 0   0 1   0 0   0 0   0 0                                       241  11.2                                                                              N  0 0   0 0   0 0   0 0   0 0                                       242  11.2                                                                              0  0 0   0 0   0 0   0 --  0 0                                       243  11.2                                                                              0  0 0   0 0   0 0   0 --  0 0                                       244  11.2                                                                              0  1 1   1 0   0 0   0 --  0 0                                       245  11.2                                                                              0  0 1   1 1   0 0   0 0   0 1                                       246  11.2                                                                              N  0 1   2 1   0 0   0 0   0 0                                       __________________________________________________________________________    Example                                                                       No.  kg/ha                                                                             L M N O P B Q D R E F C J S K T                                      __________________________________________________________________________     5   1.12                                                                              0 0 0 0 0 0 0 0 0 3 --                                                                              0 0 0 0 0                                           5.6 0 1 0 0 0 0 0 0 0 0 --                                                                              0 0 0 0 0                                       16  11.2                                                                              2 0 3 0 1 2 0 1 1 2 1 2 1 1 1 2                                           .056                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                           .28 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                           1.12                                                                              0 0 0 0 0 1 0 0 0 2 --                                                                              2 0 0 0 0                                           5.6 2 1 2 1 1 2 0 0 0 2 --                                                                              2 0 1 1 1                                      __________________________________________________________________________     *4-week observation                                                      

Compounds of this invention have been found to be extremely efficaciousas herbicides in various crops, including cotton, rice, sugarcane,sunflower, peanuts, wheat, barley, coffee, and citrus. Some of thecompounds of this invention are also particularly useful in rice. InTable 23 below, data are presented showing the effect of variouscompounds of the invention on weed species in the presence of theabove-mentioned crops.

The plant species identified by

    ______________________________________                                        Sobe   soybean         Reri     redrice                                       Cotz   cotton          Wipm     wild prosso millet                            Rrpw   redroot pigweed Bygr     barnyardgrass                                 Shca   shattercane     Yens     yellownutsedge                                Sejg   seedling johnsongrass                                                  ______________________________________                                    

The procedure utilized is that described above with respect to Tables 20and 21. Observations were made about 3 weeks after planting. Below eachplant species designation in Table 23 is listed the percent inhibitionof growth observed. As above, 100 means complete control and 0 means nocontrol.

                                      TABLE 24                                    __________________________________________________________________________    Compound                                                                            kg/ha                                                                             Sobe                                                                             Cotz                                                                             Rrpw                                                                              Shca                                                                             Sejg                                                                             Reri                                                                              Wipm                                                                              Bygr                                                                             Yens                                                                             Rice                                  __________________________________________________________________________    Ex. 67                                                                              0.56                                                                              60 0  100 100                                                                              100                                                                              98  100 100                                                                              0  100                                         0.28                                                                              40 0  40  100                                                                              100                                                                              98  100 100                                                                              0  100                                         0.14                                                                              0  0  20   95                                                                              95 70  80  100                                                                              0  100                                         0.07                                                                              0  0  0    90                                                                              80 0   70  90 0  50                                    Ex. 72                                                                              0.56                                                                              60 0  90  100                                                                              100                                                                              98  95  100                                                                              0  100                                         0.28                                                                              30 0  20   98                                                                              95 70  90  95 0  95                                          0.14                                                                              0  0  0    90                                                                              90 0   60  90 0  60                                          0.07                                                                              0  0  0    80                                                                              70 0   40  50 0  40                                    Ex. 14                                                                              0.56                                                                              95 15 95  100                                                                              100                                                                              100 100 100                                                                              90 100                                         0.28                                                                              90 0  80  100                                                                              100                                                                              100 100 100                                                                              80 100                                         0.14                                                                              80 0  50  100                                                                              100                                                                              98  100 100                                                                              0  100                                         0.07                                                                              10 0  20  100                                                                              98 80  95  100                                                                              0  98                                     Ex. 111                                                                            0.56                                                                              0  0  80   98                                                                              98 30  90  95 0  98                                          0.28                                                                              0  0  20   95                                                                              95 30  90  95 0  90                                          0.14                                                                              0  0  0    80                                                                              80 0   50  80 0  30                                          0.07                                                                              0  0  0    20                                                                              30 0    0  30 0   0                                     Ex. 110                                                                            0.56                                                                              0  0  60   98                                                                              98 40  99  98 0  90                                          0.28                                                                              0  0  0    90                                                                              90 0   80  85 0  50                                          0.14                                                                              0  0  0    80                                                                              80 0   40  70 0  30                                          0.07                                                                              0  0  0    40                                                                              50 0    0  20 0   0                                    Ex. 26                                                                              0.56                                                                              0  0  40   95                                                                              95 0   80  90 0  50                                          0.28                                                                              0  0  0    80                                                                              80 0   50  70 0  30                                          0.14                                                                              0  0  0    30                                                                              40 0    0   0 0   0                                          0.07                                                                              0  0  0    0  0 0    0   0 0   0                                    Ex. 25                                                                              0.56                                                                              40 0  90  100                                                                              100                                                                              30  100 100                                                                              0  98                                          0.28                                                                              0  0  20  100                                                                              98 0   98  100                                                                              0  80                                          0.14                                                                              0  0  0    95                                                                              95 0   90  90 0  40                                          0.07                                                                              0  0  0    80                                                                              70 0   80  85 0  30                                    Ex. 52                                                                              0.56                                                                              70 0  95  100                                                                              100                                                                              100 100 100                                                                              0  100                                         0.28                                                                              30 0  20  100                                                                              100                                                                              70  100 100                                                                              0  95                                          0.14                                                                              10 0  20  100                                                                              98 20  95  100                                                                              0  95                                          0.07                                                                              0  0  0    90                                                                              90 0   80  90 0  60                                    Ex. 53                                                                              0.56                                                                              30 0  100 100                                                                              98 80  100 100                                                                              0  100                                         0.28                                                                              10 0  30  100                                                                              100                                                                              60  98  100                                                                              0  98                                          0.14                                                                              0  0  0    85                                                                              90 0   80  80 0  50                                          0.07                                                                              0  0  0    80                                                                              70 0   50  70 0  30                                    Ex. 55                                                                              0.56                                                                              90 0  100 100                                                                              100                                                                              95  100 1001                                                                             0  100                                         0.28                                                                              80 0  98  100                                                                              100                                                                              70  100 100                                                                              0  95                                          0.14                                                                              40 0  60   98                                                                              98 40  98  100                                                                              0  95                                          0.07                                                                              0  0  0    90                                                                              85 0   90  85 0  70                                    Ex. 54                                                                              0.56                                                                              90 0  95  100                                                                              100                                                                              90  100 100                                                                              0  100                                         0.28                                                                              90 0  70  100                                                                              100                                                                              90  100 100                                                                              0  100                                         0.14                                                                              60 0  20  100                                                                              100                                                                              40  100 100                                                                              0  99                                          0.07                                                                              0  0  0    95                                                                              90 20  95  98 9  60                                     Ex. 123                                                                            0.56                                                                              0  0  0   100                                                                              98 80  95  100                                                                              0  98                                          0.28                                                                              0  0  0    95                                                                              95 20  95  95 0  80                                          0.14                                                                              0  0  0    95                                                                              85 0   60  85 0  20                                          0.07                                                                              0  0  0    30                                                                              40 0    0  30 0   0                                     Ex. 124                                                                            0.56                                                                              0  0  0    85                                                                              70 0   90  50 0  40                                          0.28                                                                              0  0  0    80                                                                              80 0   70  80 0  20                                          0.14                                                                              0  0  0    20                                                                              40 0    0  40 0   0                                          0.07                                                                              0  0  0    0  0 0    0   0 0   0                                     Ex. 101                                                                            0.56                                                                              50 0  95  100                                                                              100                                                                              20  100 100                                                                              0  20                                          0.28                                                                              30 0  60  100                                                                              100                                                                              0   100 100                                                                              0  10                                          0.14                                                                              0  0  40  100                                                                              95 0   90  100                                                                              0  15                                          0.07                                                                              0  0  0    95                                                                              95 0   70  95 0   0                                    Ex. 86                                                                              0.56                                                                              30 0  100 100                                                                              100                                                                              70  100 100                                                                              0  98                                          0.28                                                                              0  0  60  100                                                                              98 20  100 95 0  95                                          0.14                                                                              0  0  0    95                                                                              95 0   90  95 0  80                                          0.07                                                                              0  0  0    80                                                                              70 0   60  80 0  30                                    Ex. 69                                                                              0.56                                                                              90 0  100 100                                                                              100                                                                              100 100 100                                                                              0  100                                         0.28                                                                              80 0  80  100                                                                              100                                                                              98  100 100                                                                              0  100                                         0.14                                                                              20 0  0   100                                                                              100                                                                              70  100 100                                                                              0  98                                          0.07                                                                              0  0  0    90                                                                              80 20  90  90 0  90                                    Ex. 80                                                                              0.56                                                                              40 0  100 100                                                                              100                                                                              70  100 100                                                                              20 98                                          0.28                                                                              10 0  100 100                                                                              100                                                                              30  100 100                                                                              0  95                                          0.14                                                                              0  0  90   98                                                                              95 0   95  98 0  60                                          0.07                                                                              0  0  0    80                                                                              70 0   80  90 0  20                                    __________________________________________________________________________

The preemergent herbicidal activity of dimethyl 2-(difluoromethyl)-6-(trifluoromethyl)-4-isobutyl-3,5-pyridinedicarboxylatewith respect to various crop species is set forth below in Table 24.Utilizing the same procedure as described with respect to Tables 20 and21, the herbicidal effect on the crops noted in Table 24 were observedat various rates of application. The data in Table 24 indicate thatcotton has a high tolerance and peanut and sunflower have some tolerancefor this compound in that these crops were relatively unaffected by theherbicide. The herbicidal activity is noted as in Table 24 wherein 100indicates total control and 0 indicates no control. The crops listed byabbreviation are soybean (Sobe), cotton (Cotz), sugarbeet (Sube),alfalfa (Alfz), sunflower (Sufl), and peanut (Penu).

                  TABLE 25                                                        ______________________________________                                        Rate                                                                          k/ha  Sobe   Cotz   Sube  Rape Flax Alfz  Sufl Penu                           ______________________________________                                        2.4   98     50     100   100  100  100   50   80                             1.2   90     20     100   100  100  100   20   50                             .6    90     0      100   100  100  100   0    20                             .3    90     0       95   100  100  100   0    10                             .15   50     0       90    90   90   95   0     0                             ______________________________________                                    

The above tables illustrate one aspect of the present invention, thatis, the use of the compounds of the invention to kill or injureundesirable plants, e.g., weeds.

As can be seen from the data above, some of the compounds appear to bequite safe on many crops such as cotton and can thus be used forselective control of weeds in such crops.

The herbicidal compositions of this invention, including concentrateswhich require dilution prior to application, may contain at least oneactive ingredient and an adjuvant in liquid or solid form. Thecompositions are prepared by admixing the active ingredient with anadjuvant including diluents, extenders, carriers and conditioning agentsto provide compositions in the form of finely-divided particulatesolids, granules, pellets, solutions, dispersions or emulsions. Thus, itis believed that the active ingredient could be used with an adjuvantsuch as a finely-divided solid, a liquid of organic origin, water, awetting agent, a dispersing agent, an emulsifying agent or any suitablecombination of these.

Suitable wetting agents are believed to include alkyl benzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides,long chain acid esters of sodium isothionate, esters of sodiumsulfosuccinate, sulfated or sulfonated fatty acid esters, petroleumsulfonates, sulfonated vegetable oils, ditertiary acetylenic glycols,polyoxyethylene derivatives of alkylphenols (particularly isooctylphenoland nonylphenol) and polyoxyethylene derivatives of the mono-higherfatty acid esters of hexitol anhydrides (e.g., sorbitan) andpolyoxyethylene derivatives of castor oil.

Preferred dispersants are methyl cellulose,polyoxyethylene/polyoxypropylene block copolymers, polyvinyl alcohol,sodium lignin sulfonates, polymeric alkyl naphthalene sulfonates, sodiumnaphthalene sulfonate, and the polymethylene bisnaphthalene sulfonate.

Wettable powders are water-dispersible compositions containing one ormore active ingredients, an inert solid extender and one or more wettingand dispersing agents. The inert solid extenders are usually of mineralorigin such as the natural clays, diatomaceous earth and syntheticminerals derived from silica and the like. Examples of such extendersinclude kaolinites, bentonite, attapulgite clay and synthetic magnesiumsilicate. The wettable powders compositions of this invention usuallycontain from above 0.5 to 60 parts (preferably from 5-20 parts) ofactive ingredient, from about 0.25 to 25 parts (preferably 1-15 parts)of wetting agent, from about 0.25 to 25 parts (preferably 1.0-15 parts)of dispersant and from 5 to about 95 parts (preferably 5-50 parts) ofinert solid extender, all parts being by weight of the totalcomposition. Where required, from about 0.1 to 2.0 parts of the solidinert extender can be replaced by a corrosion inhibitor or anti-foamingagent or both.

Other formulations include, dust concentrates comprising from 0.1 to 60%by weight of the active ingredient on a suitable extender; these dustsmay be diluted for application at concentrations within the range offrom about 0.1-10% by weight.

Aqueous suspensions or emulsions may be prepared by stirring anonaqueous solution of a waterinsoluble active ingredient and anemulsification agent with water until uniform and then homogenizing togive stable emulsion of very finely-divided particles. The resultingconcentrated aqueous suspension is characterized by its extremely smallparticle size, so that when diluted and sprayed, coverage is veryuniform. Suitable concentrations of

these formulations contain from about 0.1-60% preferably 5-50% by weightof active ingredient, the upper limit being determined by the solubilitylimit of active ingredient in the solvent.

Concentrates are usually solutions of active ingredient inwater-immiscible or partially water-immiscible solvents together with asurface active agent. Suitable solvents for the active ingredient ofthis invention include dimethylformamide, chlorinated solvents,dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons andwater-immiscible ethers, esters or ketones. However, other high strengthliquid concentrates may be formulated by dissolving the activeingredient in a solvent then diluting, e.g., with kerosene, to sprayconcentration.

The concentrate compositions herein generally contain from about 0.1 to95 parts (preferably 5-60 parts) active ingredient, about 0.25 to 50parts (preferably 1-25 parts) surface active agent and where requiredabout 4 to 94 parts solvent, all parts being by weight based on thetotal weight of emulsifiable oil.

Granules are physically stable particulate compositions comprisingactive ingredient adhering to or distributed through a basic matrix ofan inert, finely-divided particulate extender. In order to aid leachingof the active ingredient from the particulate, a surface active agentsuch as those listed hereinbefore can be present in the composition.Natural clays, pyrophyllites, illite and vermiculite are examples ofoperable classes of particulate mineral extenders. The preferredextenders are the porous, absorptive, preformed particles such aspreformed and screened particulate attapulgite or heat expanded,particulate vermiculite and the finely-divided clays such as kaolinclays, hydrated attapulgite or bentonitic clays. These extenders aresprayed or blended with the active ingredient to form the herbicidalgranules.

The granular compositions of this invention may contain from about 0.1to about 30 parts by weight of active ingredient per 100 parts by weightof clay and 0 to about 5 parts by weight of surface active agent per 100parts by weight of particulate clay.

The compositions of this invention can also contain other additaments,for example, fertilizers, other herbicides, other pesticides, safenersand the like used as adjuvants or in combination with any of theabove-described adjuvants. Chemicals useful in combination with theactive ingredients of this invention include, for example, triazines,ureas, carbamates, acetamides, acetanilides, uracils, acetic acid orphenol derivatives, thiolcarbamates, triazoles, benzoic acids, nitriles,biphenyl ethers and the like such as:

HETEROCYCLIC NITROGEN/SULFUR DERIVATIVES

2-Chloro-4-ethylamino-6-isopropylamino-s-triazine

2-Chloro-4,6-bis(isopropylamino)-s-triazine

2-Chloro-4,6-bis(ethylamino)-s-triazine

3-Isopropyl-1H-2,1,3-benzothiadiazin-4-(3H)-one 2,2 dioxide

3-Amino-1,2,4-triazole

6,7-Dihydrodipyrido(1,2-a:2',1'-c)-pyrazidiinium salt

5-Bromo-3-isopropyl-6-methyluracil

1,1'-Dimethyl-4,4'-bipyridinium

3-methyl-4-amino-6-phenyl-1,2,4-triazin-5-(4H)one

2-(4-chloro-6-ethylamino-1,3,5-sym-2-triazinylamino)-2-methylpropionitrile

3-cyclohexyl-6-dimethylamino-l-methyl-1,3,5-triazine-2,4(1H,3H)-dione

4-amino-6-(tert-butyl)-3-methylthio-as-triazin-5(4H)one

5-amino-4-chloro-2-phenyl-3(1H)-pyridazinone

5-methylamino-4-chloro-2-(δ, δ, δ -trifluoro-m-tolyl)-3(2H)-pyridazinone

5-bromo-3-(sec-butyl)-6-methyluracil

UREAS

N-(4-chlorophenoxy) phenyl-N,N-dimethylurea

N,N-dimethyl-N'-(3-chloro-4-methylphenyl) urea

3-(3,4-dichlorophenyl)-1,1-dimethylurea

1,3-Dimethyl-3-(2-benzothiazolyl) urea

3-p-Chlorophenyl)-1,1-dimethylurea

1-Butyl-3-(3,4-dichlorophenyl)-1-methylurea

N-(3-trifluoromethylphenyl)-N,N'-dimethylurea

3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea

2-Chloro-N-([(4-methoxy-6-methyl-1,3,5-triazin--2yl)aminocarbonyl)benzenesulfonamide

Methyl2-((([(4,6-dimethyl-2-pyrimidinyl)amino]carbonyl)amino)sulfonyl)benzoate

CARBAMATES/THIOLCARBAMATES

2-Chloroallyl diethyldithiocarbamate

S-(4-chlorobenzyl)N,N-diethylthiolcarbamate

Isopropyl N-(3-chlorophenyl) carbamate

S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate

S-N,N-dipropylthiolcarbamate

S-propyl N,N-dipropylthiolcarbamate

S-2,3,3-trichloroallyl N,N-diisopropylthiolcarbamate Ethyldipropylthiolcarbamate

ACETAMIDES/ACETANILIDES/ANILINES/AMIDES

2Chloro-N,N-diallylacetamide

N,N-dimethyl-2,2-diphenylacetamide

N-(2,4-dimethyl-5-[[(trifluoromethyl)sulfonyl amino]phenylacetamide

N-Isopropyl-2-chloroacetanilide

2'6'-Diethyl-N-methoxymethyl-2-chloroacetanilide

2'-Methyl-6'-ethyl-N-(2-methoxyprop-2-yl)-2

chloroacetanilide

δ, δ, δ-Trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine

N-(1-dimethylpropynyl)-3,5-dichlorobenzamide

δ, δ, δ -Trifluoro-2,6-dinitro-N-propyl-N-(2-chloro-ethyl)-p-toluidine

3,5-Dinitro-4-dipropylamino-benzenesulfonamide

N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitro-benzenamine

ACIDS/ESTERS/ALCOHOLS

2,2-Dichloropropionic acid

2-Methyl-4-chlorophenoxyacetic acid

2,4-Dichlorophenoxyacetic acid

Methyl-2-[4-(2,4-dichlorophenoxy)phenoxy]propionate3-Amino-2,5-dichlorobenzoic acid

-Methoxy-3,6-dichlorobenzoic acid

2,3,6-Trichlorophenylacetic acid

N-1-naphthylphthalamic acid

Sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2

nitrobenzoate

4,6-Dinitro-o-sec-butylphenol

N-(phosphonomethyl) glycine and its salts

Potassium 4-amino-3,5,6-trichloropicolinate

2,3Dihydro-3,3-dimethyl-2-ethoxy-5-benzofuranyl methanesulfonate

ETHERS

2,4-Dichlorophenyl-4-nitrophenyl ether

2-Chloro- δ, δ, δ -trifluoro-p-tolyl-3-ethoxy-4-nitrodiphenyl ether

-Chloro-l-(3-ethoxy-4-nitrophenoxy)-4-trifluoromethyl benzene

MISCELLANEOUS

2,6-Dichlorobenzonitrile

Monosodium acid methanearsonate

Disodium methanearsonate

Fertilizers useful in combination with the active ingredients include,for example, ammonium nitrate, urea, potash and superphosphate. Otheruseful additaments include materials in which plant organisms take rootand grow such as compost, manure, humus, sand and the like.

Herbicidal formulations of the types described above, which includecompounds of this invention, are exemplified in several illustrativeembodiments below.

    ______________________________________                                                               Weight Percent                                         ______________________________________                                        I. Emulsifiable Concentrates                                                  A.  Compound of Example No. 14                                                                             45.6                                                 Monochlorobenzene        26.6                                                 C.sub.9 Aromatics        17.8                                                 Calcium sulfonyl benzene sulfonate                                                                     5.0                                                  Castor oil ethoxylated with 54 moles                                                                   5.0                                                                           100.0                                            B.  Compound of Example No. 101                                                                            33.7                                                 Monochlorobenzene        56.3                                                 Calcium sulfonyl benzene sulfonate                                                                     4.3                                                  Castor oil ethoxylated with 54 mols                                                                    5.7                                                                           100.0                                            C.  Compound of Example No. 5                                                                              11.0                                                 Free acid of complex organic                                                                           5.59                                                 phosphate of aromatic or aliphatic                                            hydrophobe base (e.g., GAFAC RE-610,                                          registered trademark of GAF Corp.)                                            Polyoxyethylene/polyoxypropylene                                                                       1.11                                                 block copolymer with butanol (e.g.,                                           Tergitol XH, registered trademark of                                          Union Carbide Corp.)                                                          C.sub.9 aromatics        5.34                                                 Monochlorobenzene        76.96                                                                         100.00                                           D.  Compound of Example No. 16                                                                             25.00                                                Free acid of complex organic                                                                           5.00                                                 phosphate of aromatic or aliphatic                                            hydrophobe base (e.g., GAFAC RE-610)                                          Polyoxyethylene/polyoxypropylene                                                                       1.60                                                 block copolymer with butanol (e.g.,                                           Tergitol XH)                                                                  Phenol                   4.75                                                 Monochlorobenzene        63.65                                                                         100.00                                           II. Flowables                                                                 A.  Compound of Example No. 6                                                                              25.00                                                Methyl cellulose         0.3                                                  Silica Aerogel           1.5                                                  Sodium lignosulfonate    3.5                                                  Sodium N-methyl-N-oleyl taurate                                                                        2.0                                                  Water                    67.7                                                                          100.00                                           B.  Compound of Example No. 17                                                                             45.0                                                 Methyl cellulose         .3                                                   Silica aerogel           1.5                                                  Sodium lignosulfonate    3.5                                                  Sodium N-methyl-N-oleyl taurate                                                                        2.0                                                  Water                    47.7                                                                          100.00                                           III. Wettable Powders                                                         A.  Compound of Example No. 5                                                                              25.0                                                 Sodium lignosulfonate    3.0                                                  Sodium N-methyl-N-oleyl-taurate                                                                        1.0                                                  Amorphous silica (synthetic)                                                                           71.0                                                                          100.00                                           B.  Compound of Example No. 21                                                                             80.00                                                Sodium dioctyl sulfosuccinate                                                                          1.25                                                 Calcium lignosulfonate   2.75                                                 Amorphous silica (synthetic)                                                                           16.00                                                                         100.00                                           C.  Compound of Example No. 6                                                                              10.0                                                 Sodium lignosulfonate    3.0                                                  Sodium N-methyl-N-oleyl-taurate                                                                        1.0                                                  Kaolinite clay           86.0                                                                          100.00                                           V. Dusts                                                                      A.  Compound of Example No. 2                                                                              2.0                                                  Attapulgite              98.0                                                                          100.00                                           B.  Compound of Example No. 9                                                                              60.0                                                 Montmorillonite          40.0                                                                          100.00                                           C.  Compound of Example No. 15                                                                             30.0                                                 Ethylene glycol          1.0                                                  Bentonite                69.0                                                                          100.00                                           D.  Compound of Example No. 16                                                                             1.0                                                  Diatomaceous earth       99.0                                                                          100.00                                           VI. Granules                                                                  A.  Compound of Example No. 8                                                                              15.0                                                 Granular attapulgite (20/40 mesh)                                                                      85.0                                                                          100.00                                           B.  Compound of Example No. 9                                                                              30.0                                                 Diatomaceous earth (20/40)                                                                             70.0                                                                          100.00                                           C.  Compound of Example No. 18                                                                             1.0                                                  Ethylene glycol          5.0                                                  Methylene blue           0.1                                                  Pyrophyllite             93.9                                                                          100.00                                           D.  Compound of Example No. 19                                                                             5.0                                                  Pyrophyllite (20/40)     95.0                                                                          100.00                                           ______________________________________                                    

When operating in accordance with the present invention, effectiveamounts of the compounds of this invention are applied to the soilcontaining the seeds, or vegetative propagules or may be incorporatedinto the soil media in any convenient fashion. The application of liquidand particulate solid compositions to the soil can be carried out byconventional methods, e.g., power dusters, boom and hand sprayers andspray dusters. The compositions can also be applied from airplanes as adust or a spray because of their effectiveness at low dosages.

The exact amount of active ingredient to be employed is dependent uponvarious factors, including the plant species and stage of developmentthereof, the type and condition of soil, the amount of rainfall and thespecific compounds employed. In selective preemergence application or tothe soil, a dosage of from 0.02 to about 11.2 kg/ha, preferably fromabout 0.1 to about 5.60 kg/ha, is usually employed. Lower or higherrates may be required in some instances. One skilled in the art canreadily determine from this specification, including the above examples,the optimum rate to be applied in any particular case.

The term "soil" is employed in its broadest sense to be inclusive of allconventional "soils" as defined in Webster's New InternationalDictionary, Second Edition, Unabridged (1961). Thus, the term refers toany substance or media in which vegetation may take root and grow, andincludes not only earth but also compost, manure, muck, humus, sand andthe like, adapted to support plant growth.

Although the invention is described with respect to specificmodifications, the details thereof are not to be construed aslimitations.

What is claimed is:
 1. A compound represented by the structural formula##STR48## wherein: R is selected from the group consisting of loweralkyl, lower alkenyl, lower alkynyl, lower alkenylalkyl, haloalkyl,haloalkenyl, C₃₋₇ cycloalkyl, C₃₋₆ cycloalkanylalkyl, phenyl,phenylmethyl, alkoxy-alkyl, benzyloxymethyl, alkylthioalkyl,dialkoxy-alkyl, (1-alkoxy-l-alkylthio)alkyl, aminoalkyl,alkylaminoalkyl, dialkylaminoalkyl, alkylsulfonylalkyl,alkylsulfinylalkyl, alkyl substituted with a dialkylsulfonium salt,cyanoalkyl, carbalkoxyalkyl, carbalkoxyalkenyl, alkenyl,dialkylaminoalkenyl, saturated and unsaturated heterocyclic radicalsselected from the group consisting of furyl, pyridyl, thienyl,thiiranyl, oxiranyl, and aziridinyl wherein the radical is joined to thepyridine ring by a C--C bond, and lower alkyl substituted with asaturated or unsaturated heterocyclic radical selected from the groupconsisting of furyl, pyridyl, thienyl, thiranyl, oxiranyl, andazirdinyl;R₁ and R₂ are independently selected from alkyl, fluorinatedmethyl, and chlorofluorinated methyl radicals, provided that one of R₁and R₂ must be a fluorinated methyl or chlorofluorinated methyl radical;and X and Y are independently selected from the group consisting of##STR49## where Z₁ is NR₇ where R₇ is selected from hydrogen and loweralkyl and wherein Z₂ is selected from O and S, and wherein R₃ is eachoccurrence is independently selected from hydrogen, alkyl C₁₋₄₆,alkenylalkyl C₃₋₄, haloalkyl C₁₋₄, cyanoalkyl, cycloalkanylalkyl,alkynylalkyl C₃₋₄, provided that when Z₂ is S is both occurrences, R₃must be lower alkyl C₁₋₂ ; ##STR50## wherein R₄ is selected fromhydrogen and halogen; ##STR51## wherein R₅ and R₆ are independentlyselected from hydrogen, lower alkyl, and phenyl; --CH₂ OH and --C.tbd.N.2. A compound according to claim 1 wherein one of R₁ and R₂ is atrifluoromethyl radical and the other is a fluorinated methyl radical.3. A compound according to claim 1 wherein one of R₁ and R₂ is atrifluoromethyl radical and the other is an alkyl radical.
 4. Aherbicidal composition containing a herbicidally effective amount of acompound represented by the structural formula ##STR52## wherein: R isselected from the group consisting of lower alkyl, lower alkenyl, loweralkynyl, lower alkenylalkyl, haloalkyl, haloalkenyl, C₃₋₇ cycloalkyl,C₃₋₆ cycloalkanylalkyl, phenyl, phenylmethyl, alkoxy-alkyl,benzyloxymethyl, alkylthioalkyl, dialkoxy-alkyl,(1-alkoxy-1-alkylthio)alkyl, aminoalkyl, alkylaminoalkyl,dialkylaminoalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, alkylsubstituted with a dialkylsulfonium salt, cyanoalkyl, carbalkoxyalkyl,carbalkoxyalkenyl, dialkylaminoalkenyl, saturated and unsaturatedheterocyclic radicals selected from the group consisting of furyl,pyridyl, thienyl, thiiranyl, oxiranyl, and aziridinyl wherein theradical is joined to the pyridine ring by a C--C bond, and lower alkylsubstituted with a saturated or unsaturated heterocyclic radicalselected from the group consisting of furyl, pyridyl, thienyl,thiiranyl, oxiranyl, and aziridinyl;R₁ and R₂ are independently selectedfrom alkyl, fluorinated methyl, and chlorofluorinated methyl radicals,provided that one of R₁ and R₂ must be a fluorinated methyl orchlorofluorinated methyl radical; and X and Y are independently selectedfrom the group consisting of ##STR53## wherein Z₁ is NR₇ where R₇ isselected from hydrogen and lower alkyl and wherein Z₂ is selected from Oand S, and wherein R₃ in each occurrence is independently selected fromhydrogen, alkyl C₁₋₄, alkenyl C₃₋₄, haloalkyl C₂₋₄, cyanoalkyl,cycloalkanylalkyl, and alkynylalkyl C₃₋₄, provided that when Z₂ is S inboth occurrences, R₃ must be lower alkyl C₁₋₂ ; ##STR54## wherein R₄ isselected from hydrogen and halogen; ##STR55## wherein R₅ and R₆ areindependently selected from hydrogen, lower alkyl, and phenyl; --CH₂ OH;and --C.tbd.N.
 5. A herbicidal method comprising applying to the plantlocus an effective amount of a compound represented by the structuralformula ##STR56## wherein: R is selected from the group consisting oflower alkyl, lower alkenyl, lower alkynyl, lower alkenylalkyl,haloalkyl, haloalkenyl, C₃₋₇ cycloalkyl, C₃₋₆ cycloalkanylalkyl, phenyl,phenylmethyl, alkoxyalkyl, benzyloxymethyl, alkylthioalkyl,dialkoxyalkyl, (I-alkoxy-l-alkylthio)alkyl, aminoalkyl, alkylaminoalkyl,dialkylaminoalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, alkylsubstituted with a dialkylsulfonium salt, cyanoalkyl, carbalkoxyalkyl,carbalkoxyalkenyl, dialkylaminoalkenyl, saturated and unsaturatedheterocyclic radicals selected from the group consisting of furyl,pyridyl, thienyl, thiiranyl, oxiranyl, and aziridinyl wherein theradical is joined to the pyridine ring by a C--C bond, and lower alkylsubstituted with a saturated or unsaturated heterocyclic radicalselected from the group consisting of furyl, pyridyl, thienyl, thiianyl,oxiranyl, and aziridinyl;R₁ and R₂ independently selected from alkyl,fluorinated methyl, and chlorofluorinated methyl radicals, provided thatone of R₁ and R₂ must be a fluorinated methyl or chlorofluorinatedmethyl radical; and X and Y are independently selected from the groupconsisting of ##STR57## wherein Z₁₂ is NR₇ where R₇ is selected fromhydrogen and lower alkyl and wherein Z₂ is selected from O and S, andwherein R₃ in each occurrence is independently selected from hydrogen,alkyl C₁₋₄, alkenylalkyl C₃₋₄, haloalkyl C₂₋₄, cyanoalkyl,cycloalkanylalkyl, and alkynylalkyl C₃₋₄, provided that when Z₂ is S isboth occurrences, R₃ must be lower alkyl C₁₋₂ ; ##STR58## wherein R⁴ isselected from hydrogen and halogen; ##STR59## wherein R₅ and R₆ areindependently selected from the hydrogen, lower alkyl, and phenyl; --CH₂OH; and --C.tbd.N.